CN1084552A

CN1084552A - Sulfurized overbased compositions

Info

Publication number: CN1084552A
Application number: CN93117354A
Authority: CN
Inventors: J·M·卡洪; J·L·卡尼; N·Z·黄; J·P·罗斯基
Original assignee: Lubrizol Corp
Current assignee: Lubrizol Corp
Priority date: 1992-09-04
Filing date: 1993-09-03
Publication date: 1994-03-30
Also published as: EP0586258A3; DE69331211T2; ATE209673T1; AU4608093A; JPH06166887A; EP0586258B1; CA2105314A1; US5484542A; ZA936401B; CA2105314C; PL300292A1; IL106863A0; MX9305120A; BR9303145A; CZ178493A3; EP0586258A2; DE69331211D1; KR940007164A; AU670113B2

Abstract

The present invention relates to comprise the composition of at least a sulfurized high alkalinity product, sulfuration high alkalinity product is with the preparation that contacts with (B) sulphur and/or at least a sulphur source of (A) at least a high alkalinity product or (A ') at least a boracic high alkalinity product; High alkalinity product (A) or boracic high alkalinity product (A ') are to prepare with at least a acidic substance, sulfuration high alkalinity product is heat-staple, in lubricant, sense liquid and conventional liq fuel, be used as extreme pressure agent (EP) and/or anti-wear agent or antioxidant, be specially adapted to gear lubricant and cutting fluid.

Description

Sulfurized overbased compositions

The present invention relates to sulfurized high alkalinity product, it can be used as spy's (height) and presses (power) (EP) and/or wear preventive additive or oxidation inhibitor and be used for lubricant, functional liquid and common liquid fuel.Functional liquid can be oil base, water-oil emulsion or water base.These sulfurized high alkalinity products are heat-staple, are particularly suitable for being used for gear lubricant and cutting fluid as EP and/or wear preventive additive.

On automobile and bogie market, constantly require to have littler lighter thrust unit, this is just then require to have littler lighter engine and drive transmission part (for example wheel box, axostylus axostyle etc.).Because they are lighter littler, so these engines and drive transmission part must be operated under higher speed, so, except that other thing, just cause requirement to have the lubricant of improved EP/ abrasion resistance and high-temperature stability characteristic.

The example of the EP/ wear preventive additive that uses in this field has the chlorating fat hydrocarbon such as chlorinated wax so far; Organic sulfide and polysulfide such as benzyl disulfide, two (benzyl chloride base) two sulphur, dibutyl four sulphur, sulfurized Witconol 2301, sulfurized alkylphenol, sulfurized limonene and sulfurized terpene; The reaction product of phosphorus sulfurized hydro carbons such as phosphoric sulfide and turps or Witconol 2301; Phosphorous acid esters mainly comprise the phenylester of phosphorous acid dialkyl ester and trialkyl ester such as dibutyl phosphite, phosphorous acid two heptyl esters, phosphorous acid dicyclohexyl ester, phosphorous acid amyl group phenylester, phosphorous acid diamyl phenylester, tridecyl phosphite, phosphorous acid distearyl ester, phosphorous acid dimethyl naphthyl ester, phosphorous acid oil base 4-amyl group phenylester, phosphorous acid polypropylene (molecular weight 500)-replacement, phenylester, the thiocarbamate metal-salt that the phosphorous acid diisobutyl replaces, such as dioctyl zinc dithiocarbamate and heptyl phenyl dithiocarbamic acid barium; The II family metal-salt of phosphorodithioic acid is such as the dicyclohexyl zinc dithiophosphate, the dioctyl zinc dithiophosphate, two (heptyl phenyl)-phosphorodithioic acid barium, dinonyl phosphorodithioic acid cadmium, and by the zinc salt of thiophosphoric anhydride with the phosphorodithioic acid of the mixture reaction generation that waits mole Virahol and n-hexyl alcohol.

Washing composition/the dispersion agent that is used for the generation ash in this field so far comprises by basic metal or alkaline-earth metal and sulfonic acid, formed oil-soluble neutral salt of carboxylic acid and some organic phosphoric acids and high alkalinity salt.Term " high alkalinity " salt here is to be used to refer to such metal-salt, and the amount that metal wherein exists is greater than the amount of organic acid on stoichiometry.

By at elevated temperatures (for example, 60-300 ℃) to prepare high alkalinity salt be known to the following reaction mixture of contact, should comprise at least a in this reaction mixture by the organic substance of high alkalinityization (sulfonic acid for example, carboxylic acid, phenol, the organic phosphorous acid of some classification), a kind of mainly comprise at least a for above-mentioned inert organic solvents/thinner of being used by the organic substance of high alkalinityization (for example mineral oil), the excessive at least a metal base of stoichiometry (sodium hydroxide for example, calcium hydroxide, magnesium oxide), at least a promotor (for example methyl alcohol, phenol) and at least a acidic substance (CO for example ₂, SO ₂).The method for preparing these high alkalinity salt and various kinds high alkalinity salt is that Yi Zhi De And exists in this specialty, for example, is disclosed in the following United States Patent (USP): 2,616,904; 2,616,905; 2,616,906; 2,616,911; 2,616,924; 2,616,925; 2,617,049; 2,695,910; 2,723,234; 2,723,235; 2,723,236; 2,760,970; 2,767,164; 2,767,209; 2,777,874; 2,798,852; 2,839,470; 2,856,359; 2,859,360; 2,856,361; 2,861,951; 2,888,340; 2,915,517; 2,959,551; 2,968,642; 2,971,014; 2,989,463; 3,001,981; 3,027,325; 3,070,581; 3,108,960; 3,147,232; 3,133,019; 3,146,201; 3,152,991; 3,155,616; 3,170,880; 3,170,881; 3,172,855; 3,194,823; 3,223,630; 3,232,883; 3,242,079,3,242,080; 3,250,710; 3,256,186; 3,274,135 and 3,492,231.

By M.W.Ranney write, Noyes Data Corporation of Parkridge, N.J. publish the book of " lubricant additive " (" a Lubricant Additives ") by name of (1973), disclose some high alkalinity metal salt that formed by multiple sulfonic acid, carboxylic acid and phenols, they can be as washing composition/dispersion agent in lube product.Also have one by C.V.Smallheer and R.K.Smith write, Lezius-Hiles Co.of Cleveland, Ohio publishes the book of being also referred to as of (1967) " lubricant additive " (Lubricant Additives "), discloses some similarly and can be used as the high alkalinity salt of sulfonic acid, phenols and the carboxylic acid of dispersion agent.United States Patent (USP) 4,100,082 neutral salt or the high alkalinity salt that discloses the acid of use organic sulfur-containing, carboxylic acid and phenols is used for fuel and lubricating oil as washing composition/dispersion agent.United States Patent (USP) 4,627, the 928 high alkalinity magnesium salts that disclose the aromatic hydroxycarboxylic acid of use replacement are used for lubricating oil and fuel as dispersion agent, washing composition or oxidation inhibitor.

English Patent 1,242,102 disclose a kind of method, and it is included under 20 ℃ the temperature following material is contacted at least: (a) at least a mineral acid that is selected from, the compound of their ammonia salt, amine salt and metal-salt and mineral acid gas (SO for example ₂), the latter can form the acid stronger than carbonic acid in water; (b) at least a high alkalinity, the complex compound that contains I or II family metal of carbonatization; Require to have at least a kind of peptizing agent to exist during contact, it comprises a kind of is effective material as dispersion agent in lubricating oil, but be not the organic complex that contains I family or second family metal of a kind of high alkalinity, carbonatization, (a) that should be able to make at least one part duration of contact with (b) react.

United States Patent (USP) 4,507,215 and 4,579,666 disclose a kind of composition, and it comprises: (A) at least a acid neutrality or overbased metal salt with acid (A) (I) of following formula:

Wherein each X and X ¹Can represent oxygen or sulphur independently, each n is zero or one, each R ¹Can represent identical or different alkyl independently; With at least a acidity that contains the carboxylic acid (A) (II) of about 2 to 40 carbon atoms, neutrality or overbased metal salt (A) (I) equivalent to the normal ratio of (A) (II) at about 0.5: 1 to about 1: 0 scope; (B) a kind of alefinically unsaturated compounds that can react with active sulphur.Containing the composition of above-mentioned component and the reaction of active sulphur is disclosed.The lubricant and the sense liquid that contain above-mentioned composition are disclosed.The method that the following active sulphur of condition that exists at component (A) and a kind of alefinically unsaturated compounds react also is disclosed.

International monopoly WO89/04358 discloses a kind of composition, it comprises the neutrality or the overbased metal salt of the boracic of (A) at least a neutrality or overbased metal salt or at least a acidic organic compound, metal can be selected from basic metal in said salt, alkaline-earth metal, zinc, copper, the mixture of aluminium or two or more said metals; (B) at least a metal deactivator; (C) at least a dithiocarbamate (C-3) that contains phosphamide (C-1), phosphorated ester class (C-2), coupling sulphur that is selected from, the organic compound that the part of the coupling sulphur that can be expressed from the next replaces:

R wherein ¹, R ², R ³And R ⁴Represent H or alkyl independently of one another; R ¹And/or R ³Can be G ¹Or G ²; R ¹And R ²And/or R ³And R ⁴Can be to contain about 4 alkylidene groups to about 7 carbon atoms together; G ¹And G ²Represent C(X independently of one another) R, COOR, C ≡ N, R ⁵-C=NR ⁶, CON(R) ₂Or NO ₂, G ¹Also can be CH ₂OH, wherein X is O or S, each R and R ⁵Can represent H or an alkyl independently, R ⁶Be H or an alkyl; Work as G ¹And G ²The both is R ⁵C=NR ⁶The time, these two groups can be alkyl that connects these two nitrogen-atoms together; Work as G ¹Be CH ₂OH, G ²When being COOR, G ¹And G ²Can form lactone by intramolecular condensation; X be one by 1 to about 8 integer; (C) two or more mixtures of forming (C-5) in the also optional freedom (C-1) to (C-4).These compositions can be used as additive and are used for lubricant and sense liquid, in products such as hydraulic fluid, gear oil, lubricating grease.

United States Patent (USP) 4,755,311 disclose with elementary sulfur or various energy and provide in the reaction sulphur source of sulphur to prepare the method for monothio phosphoric acid.Disclosed sulphur source comprises halogenation sulphur in this bibliography, fragrance and alkyl sulfur compounds, dialkylene sulfide, sulfurized alkene, vulcanized oil, sulfurized fatty acid ester, sulfurized contain the monobasic of ethylene linkage or the fatty group ester of di-carboxylic acid, diester sulfide, sulfurized Diels-Alder adduct and sulfurized terpene.

The present invention relates to contain the composition of at least a sulfurized high alkalinity product, it is with (B) sulphur and/or at least a sulphur source make by the high alkalinity product of contact (A) at least a overbasic product or (A ') at least a boracic.The high alkalinity product (A ') of said high alkalinity product (A) or boracic makes with at least a acid material, condition be when said acid material be not SO ₂Or SO ₂During the source, the high alkalinity product (A ') of said high alkalinity product (A) or boracic should with the SO of significant quantity ₂Or SO ₂The source contact is to replace the said acid material of at least one part.Sulfurized high alkalinity product is the high alkalinity thiosulphate of a kind of overbasic thiosulphate or boracic in a specific embodiments.Sulfurized high alkalinity product is to make with high alkalinity product (A) and the composition that further comprises the boracic high alkalinity product of at least a unvulcanised in a specific embodiments.This sulfurized high alkalinity product is thermally-stabilised And to be can be used as EP and/or wear preventive additive or oxidation inhibitor be used for lubricating oil, in sense liquid and the common liquid fuel.Sense liquid can be oil base, 1K-oil emulsion or water base.This sulfurized high alkalinity product is particularly suitable for as EP and/or wear preventive additive and is used for gear lubricant and cutting fluid.The lubricant compositions that provides in a specific embodiments has passed through the wear-resistant system that the high torsional moment test of L-37 and L-42 high speed shaking test need not to use in the prescription at them phosphorous and olefine sulfide.

In this specification sheets and appended claim, use term " alkyl " to refer to such group, it has a carbon atom directly to connect all the other ， And and have the characteristic of hydro carbons or mainly have the characteristic of hydro carbons in context of the present invention partly to molecule, and this class group comprises:

(1) alkyl; Promptly (for example cycloalkyl or the cycloalkenyl group) of Zhi Fang (for example alkyl or alkenyl), alicyclic ring, fragrance, fat-and the fragrance of alicyclic ring-replacements, the fat of fragrance replacement or alicyclic ring or the like; And the cyclic group, ring wherein is other (in other words, any two substituting groups of pointing out can form an alicyclic radical together) that partly forms by molecule.This class group is known for these professional those skilled in the art.Embodiment comprises methyl, ethyl, octyl group, decyl, octadecyl, cyclohexyl, phenyl etc.

(2) alkyl of Qu Daiing; The group that promptly contains non-hydrocarbon substituent, what it can not change group in the context of the present invention mainly is the attribute of hydrocarbon polymer.These professional those skilled in the art will be appreciated that this class suitable substituents.Example comprises halogen, hydroxyl, nitro, cyano group, alkoxyl group, acyl group etc.

(3) assorted base; Be such group, the attribute of its main performance hydro carbons in the scope of the context of the invention, but in the carbochain of forming them or carbocyclic ring, also contain carbon atom in addition simultaneously.Suitable heteroatoms is conspicuous for those skilled in the art, comprises, for example nitrogen, oxygen and sulphur.

Generally, do not have more than about three substituting groups or heteroatoms, preferably no more than one in per 10 carbon atoms that in alkyl, exist.

Term is such as " based on alkyl ", and " based on aryl " or the like has and similar connotation such as abovementioned alkyl, aryl.

Term " based on hydrocarbon " is when being used to refer to when having a molecular radical that directly connects to all the other carbon atoms partly of molecule, with the connotation of term " alkyl " Xiang Tong And can use with " alkyl " exchange.

Here with alkyl, alkyl, alkenyl, terms such as alkoxyl group connect the term " rudimentary " that uses, and are to be used for describing containing this class group that sum is no more than 7 carbon atoms.

Term " oil-soluble " is used to refer to a kind of material, and its dissolved degree in mineral oil at least approximately restrains at every liter 1 in the time of 25 ℃.

High alkalinity product (A):

Term " overbasic " is the general name of this specialty for metal-salt of knowing or complex compound compounds.These materials are also referred to as " alkalescence ", " hyperalkaline ", " peralkaline ", " complexing ", " metal complex ", " salt of high metal content " or the like.Overbasic product is such metal-salt or complex compound, it is characterized by to contain than according to metal and concrete and acidic organic compound metal reaction, and sulfonic acid for example, carrying out stoichiometric result is excessive metal.For example, come with a kind of alkali metal compound such as calcium hydroxide in and monobasic sulfonic acid:

" neutral " that is produced or " normally " metal-salt should be the calcium that contains monovalent for every normal acid, that is:

But as well-known in this specialty, can there be the whole bag of tricks to obtain containing the solution that the product more than the stoichiometry metal forms in a kind of inert organic liquid.The solution of these products is called as overbasic product or material here.According to these schedule of operation, sulfonic acid or its a kind of basic metal or alkaline earth salt can react And with metal base and product will contain above the required metal content of this acid of neutralization, is for example having the metal of 4.5 times of as many as to exist in normal salt, in other words the excessive 3.5 times of equivalents of metal.Actual surpass stoichiometric amount of metal and can in very large range change, for example depend on the factors such as condition of reaction, method, can be normal excessive by about 0.1 times of equivalent extremely about 40 times or more times.

Term " metal ratio " here is to be used to refer to according to the stoichiometry of known chemically reactive and two kinds of reactants to calculate, in overbased material (for example a kind of sulfonate of metal or carboxylate salt) total chemical equivalent of metal to product in stoichiometric ratio of metal, estimate when this product is reacted between organic materials of high alkalinityization (for example sulfonic acid or carboxylic acid) and the metallic reactant (for example calcium hydroxide, barium oxide etc.) to form.For example, in the normal calcium sulphonate of Tao Luning, the metal ratio is 1 in the above, and in above-mentioned overbasic sulfonate, the metal ratio is 4.5.Obviously, if in by the material of high alkalinityization, exist more than a kind of can with the compound of metal reaction, then " metal ratio " of product will to depend on the equivalents of metal in the product of high alkalinityization be to compare with the equivalents that exists by the single component that provides, still the equivalents that combines by all components that provide comes comparison.

Component (A) typically has and surpasses 1 metal Bi Li And and generally can be up to about 40 or higher.The metal ratio of component (A) is by surpassing 1 to about 35, more preferably by surpassing 1 to about 30 in a specific embodiments.The scope of preferred metal ratio is by about 1.1 or about 1.5 to about 40, more preferably about 1.1 or about 1.5 to about 35, more preferably about 1.1 or about 1.5 to about 30, more preferably about 1.1 or about 1.5 to about 26. in a specific embodiments metal ratio be by about 1.5 to about 30, more preferably about 6 to about 30, more preferably about 10 to about 30, more preferably about 15 to about 30.In a specific embodiments, metal ratio is by about 20 to about 30, more preferably about 23 to about 27, more preferably about 25.

In a specific embodiments, overbasic product (A) prepares by contacting following reaction mixture, and it comprises (A) (I), and is at least a by the organic materials of high alkalinityization; (A) (II), a kind of is the said reaction medium of being used by the organic materials of high alkalinityization, it mainly contains at least a inert organic solvents/thinner; (A) (III), at least a metal base that stoichiometry is excessive; (A) (IV), at least a promotor; (A) (V), at least a acid material.The method for preparing the high alkalinity product of this high alkalinity product (A) and various kinds is many known And in prior art and has been disclosed, in for example following United States Patent (USP):

2,616,904; 2,616,905; 2,616,906; 2,616,911; 2,616,924; 2,616,925; 2,617,049; 2,695,910; 2,723,234; 2,723,235; 2,723,236; 2,760,970; 2,767,164; 2,767,209; 2,777,874; 2,798,852; 2,839,470; 2,856,359; 2,859,360; 2,856,361; 2,861,951; 2,883,340; 2,915,517; 2,959,551; 2,968,642; 2,971,014; 2,989,463; 3,001,981; 3,027,325; 3,070,581; 3,108,960; 3,147,232; 3,133,019; 3,146,201; 3,152,991; 3,155,616; 3,170,880; 3,170,881; 3,172,855; 3,194,823; 3,223,630; 3,232,883; 3,242,079; 3,242,080; 3,250,710; 3,256,186; 3,274,135; With 3,492,231.

These patent disclosures method, can be by the organic materials of high alkalinityization, suitable metal base, promotor, acid material and many concrete high alkalinity products that can be used to produce the high alkalinity product (A ') of high alkalinity product (A) that the present invention uses or boracic, therefore, they are herein incorporated as the reference data.

By the organic materials of high alkalinityization (A) (I):

By a key property of the organic materials of high alkalinityization (A) (I) is its solubleness in being used for the specific reaction medium (A) (II) of high alkalinity process.When reaction medium (A) (II) is a kind of petroleum cuts, during mineral oil, be oil-soluble particularly by the organic materials of high alkalinityization (A) (I).But if use other reaction medium (for example aromatic hydrocarbon, aliphatic hydrocarbon, kerosene etc.), then as long as be soluble by the organic materials of high alkalinityization in the reaction medium that provides, it is to be dissolved in that this point is not a particularly important just in the mineral oil.Obviously, there are many organic materialss both to dissolve in the mineral oil, also dissolve in many other specified suitable reaction mediums.When indicating the solubleness of organic materials (A) (I) in reaction medium (A) (II), be to be understood that organic materials (A) (I) soluble degree in reaction medium (A) (II) should be that 1 gram material (A) (I) is arranged in every liter medium (A) (II) at least in the time of 25 ℃.Term " oil-soluble " here and in whole patent specification and appended claim, all be to be used to refer to such material, its dissolved degree in mineral oil reaches in the time of 25 ℃ at least the said material of 1 gram in the said mineral oil of every liter.

By the organic materials of high alkalinityization preferably have at least a kind of be carboxylic acid (A) (I) (a), the acid of sulfur-bearing (A) (I) (b), phosphorated acid (A) (I) (c), functional group's substituted aromatics (A) (I) (d), active methylene compound (A) (I) (e), the organic compound (A) (I) that replaces with the functional group of sulphur coupling (f), the precursor of any above-claimed cpd or the mixture of forming by two or more any above-claimed cpds or precursor.These generally are oil-soluble organic acids, comprise phosphonothious acid, thiocarboxylic acid or the like.Also comprise their corresponding alkali metal salt and alkaline earth salts.These organic acids and the representational example of other organic acid, for example nitronic acid, arsenic acid etc. and the method for preparing the high alkalinity product by them together, be disclosed in the patent documentation of quoting as proof below, these patents are herein incorporated as the reference data.United States Patent (USP) 2,616,904; 2,695,910; 2,767,164; 2,767,209; 3,147,232; 3,274,135 grades disclose many organic carboxyl acids that are suitable for preparing overbased material and by the example of the representational high alkalinity product of this class acid preparation.In United States Patent (USP) 2,883,340; 2,915,517; 3,001,981; 3,108,960; With 3,232, the acid of some high alkalinityizatioies is disclosed in 883, acid wherein is phosphonous acid, phosphonothionic acid, the combination of the acid of phosphonous acid-sulfur-bearing and the acid of sulfur-bearing by the Polyene Hydrocarbons preparation.Overbasic phenates is disclosed United States Patent (USP) 2,959, and in 551, overbasic ketone then is found in United States Patent (USP) 2,798,852.Many by oil-soluble, metal-free, can not tautomeric neutrality and alkaline polar organic compounds, such as the ester class, amine, amides, alcohols, ethers, the thioether class, institute's deutero-overbased material such as sulfoxide class have been disclosed United States Patent (USP) 2,968,642; 2,971,014; With 2,989, in 463.Polyalkenes such as the polyethylene that can be replaced of other classification, polypropylene, polyisobutene etc. by the fat hydrocarbon, particularly nitro that the material of high alkalinityization have oil-soluble, nitro to replace.Such material is at United States Patent (USP) 2,959, illustrated in 551.Equally, alkylating trimethylene diamine of alkylene polyamine class such as trimethylene diamine or N-and formaldehyde maybe can produce compound (for example Paraformaldehyde 96) reaction of formaldehyde and the oil soluble product that forms also can be by high alkalinityization.Other compound that is suitable for high alkalinityization also is disclosed in the patent documentation of quoting as proof above, or this specialty is well-known.

Carboxylic acid (A) (I) is (a):

Being used as by the carboxylic acid of the organic materials of high alkalinityization (A) (I) in preparation high alkalinity product (A) can be fat or fragrant monobasic or polycarboxylic acid or acidic compound (a).In whole patent specification and appended claim, unless stated otherwise, any compound that is indicated as being carboxylic acid all comprise those can acidic derivative such as acid anhydrides, the mixture of ester, carboxylic acid halides, lactone and above-mentioned these materials.

Carboxylic acid (A) (I) (a) dissolves in reaction medium (A) (II) Zhong ， And and in a specific examples scheme, carboxylic acid (A) (I) is oil-soluble (a).The carbon atom number that is present in the carboxylic acid molecules is very important to giving this molecule with needed solubleness.Generally, for required solubleness is provided, the number of carbon atom should have about 8 carbon atoms at least in the carboxylic acid molecules.These carboxylic acids can have about at least 12 carbon atoms, or about at least 16 carbon atoms, or about at least 20 carbon atoms, or about at least 30 carbon atoms, or about at least 50 carbon atoms.Generally, can not comprise in each molecule of these carboxylic acids more than about 400 or about 500 carbon atoms.

In a specific embodiments, carboxylic acid is carboxylic acid or the acid anhydrides that has the available following formula representative of an alkyl replacement at least:

Wherein R is a fully long alkyl, and it dissolves in the reaction medium (A) (II) carboxylic acid or acid anhydrides.In a specific embodiments R be one contain about at least 8 carbon atoms, be more preferably about at least 12 carbon atoms, the alkyl of about at least 16 carbon atoms preferably.Having number average molecular weight (Mn) is that the scope of the Mn value that has of useful And and these alkyl can from about 200 to about 4000 at least 200 alkyl, or from about 500 to about 3000, or from about 700 to about 2500.Alkyl R can be selected from following compound derived from least a, comprises ethene, propylene, 1-butylene, iso-butylene, 1-amylene, 2-methyl-1-butene alkene, 3-methyl-1-butene, the 1-hexene, 1-heptene, 1-octene, vinylbenzene, 1-nonene, 1-decene, the 1-undecylene, 1-dodecylene, 1-tridecylene, tetradecene, 1-15 carbenes, cetene, the 1-heptadecene, the 1-vaccenic acid.Also available higher alkenes mixture is such as containing about 18 alkene to about 24 carbon atoms.Alkyl R can be selected from following alpha-olefin fraction derived from least a, comprises C _15-18Alpha-olefin, C _12-16Alpha-olefin, C _14-16Alpha-olefin, C _14-18Alpha-olefin and C _16-18Alpha-olefin.R is an alkyl or a thiazolinyl in a specific embodiments.R is a polypropylene in a specific embodiments, polybutene, polyisobutene or the mixture that is formed by two or more said polyolefins.In a specific embodiments, R is R ¹* (R " O) nR ' ", wherein R ' is an alkyl, preferably one contains 1 to about 200 carbon atoms or about 4 aliphatic groups to about 100 carbon atoms; R " is ethene or propylene; R ' " be an alkylidene group, it preferably contains about at the most 30 carbon atoms, and one or about at the most 20 carbon atoms, or about at the most 10 carbon atoms, or about at the most 4 carbon atoms, or about at the most 2 carbon atoms, or only contain a carbon atom; X is O, S or R " N ", and wherein R " " is hydrogen or alkyl, preferably hydrogen or a lower alkyl are more preferably hydrogen or a low alkyl group; N is between zero to about 10, or between zero to about 6, or the number between zero to about 3.Also available these sour lower alkyl esters.

Carboxylic acid can contain the polar substituting group, as long as polar substituent is not to exist so that changed the hydrocarbon properties of carboxylic acid greatly with enough big some.Typical suitable polar substituent comprises halogen; such as chlorine and bromine, oxo, hydroxyl, formyl radical, sulfinyl, sulfinyl, sulfo-, nitro etc.; this class polar substituent, if exist, preferably be no more than by weight carboxylic acid except that carboxyl alkyl part gross weight about 10%.

It is desirable to will with monocarboxylic acid comprise saturated and undersaturated acid.The enforcement of the carboxylic acid that this class is useful comprises lauric acid, palmitinic acid, capric acid, oleic acid, lauric acid, stearic acid, tetradecanoic acid, linolic acid, linolenic acid, naphthenic acid, chloro stearic acid, tall oil acid etc.Also available these sour acid anhydrides and lower alkyl esters, the mixture of also available two or more these class reagent.Extensive detailed discussion to these acids can be referring to " chemical industry complete works " (" Encyclopedia of Chemieal Technoloy ") third edition that Kirk-Othmer write, (1978) John Wiley ﹠amp; Sons New York, the 814-871 page or leaf; This part content is incorporated in herein by bibliography.Polycarboxylic acid comprises di-carboxylic acid and derivative thereof, such as sebacic acid hexadecyl propanedioic acid, and the Succinic anhydried that four propylidene replace etc.

Also these carboxylic acid halides of the carboxylic acid halides of available above-mentioned carboxylic acid can be by the acid of this class or their acid anhydrides and halide reagent such as phosphorus tribromide, phosphorus pentachloride, and phosphorus oxychloride or thionyl chloride are reacted and made.The ester class of this class acid can be simply by carboxylic acid, carboxylic acid halides or acid anhydrides and alcohol or phenolic compound reaction are made.Useful especially is low alkyl group and alkenyl alcohol such as methyl alcohol, ethanol, allyl alcohol, propyl alcohol, and the common available basic catalyst of esterifications such as hexalin is such as sodium hydroxide or alkoxide sodium, or a kind of an acidic catalyst such as sulfuric acid or toluenesulphonic acids promote.

Monocarboxylic acid comprises different lipid acid, and promptly those contain the carboxylic acid of one or more rudimentary non-annularity side chain alkyl.This class acid often comprises one to have by about 14 to the main chain of about 20 saturated fatty carbon atoms and at least one but the common non-annularity alkyl of no more than about 4 side chains.The example of the main chain that these are sour can be derived from n-tetradecane, pentadecane, hexadecane, heptadecane, octodecane and twenty carbon alkane side-chain radical preferably a low alkyl group such as methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the group side-chain radical that the tertiary butyl, n-hexyl or other contain maximum 7 carbon atoms also can be the alkyl of a polar substitution such as the chloro methyl, the bromo butyl, methoxy ethyl etc., but the specific embodiments that had better not comprise in each group more than the different lipid acid of this class of polar substituent comprises 10-methyl-ten tetra-carbonic, 11-methyl-15 carbonic acid, 3-ethyl-16 carbonic acid, 15-methyl-17 carbonic acid, 16-methyl-17 carbonic acid, 6-methyl-18 carbonic acid, 8-methyl-18 carbonic acid, 10-methyl-18 carbonic acid, 14-methyl-18 carbonic acid, 16-methyl-18 carbonic acid, 15-ethyl-17 carbonic acid, 3-chloromethyl-19 carbonic acid, 7,8,9,10-tetramethyl--18 carbonic acid, and 2,9,10-trimethylammonium-18 carbonic acid.

Different lipid acid also comprises by commodity lipid acid, for example contains the mixture of the about 16 band fork chain acid that make through isomerization to the lipid acid of about 18 carbon atoms.A kind of useful method be lipid acid about more than 250 ℃ temperature and about 200 to 700psi pressure under heat, distilling out that the isomerized Suan ， of crude product And produces distillate hydrogenation is saturated through isomerized acid substantially.Isomerization reaction can be by catalyzer such as inorganic clay, diatomite, and aluminum chloride, zinc chloride, iron(ic) chloride or some other Friedel-Craft catalyst for reaction promote.Catalyst concentration can be low to moderate 0.01%, but more generally be also can promote isomerization reaction with about 0.1% to about 3%1K of isomeric mixtures weight, about by weight 0.1% to about 5% the water that therefore adds a small amount of in the isomeric mixtures is good.Can comprise oleic acid, linolic acid, linolenic acid and commodity fatty acid mixt such as tall oil acid etc. by the unsaturated fatty acids that it derives different lipid acid.

Being suitable for as the carboxylic acid that is replaced by the alkyl of the organic materials of high alkalinityization is that well-known ， And exists in this specialty, and for example Yi Xia United States Patent (USP) is at large described in English Patent and the Canadian Patent: 3,024,237; 3,087,936; 3,163,603; 3,172,892; 3,215,707; 3,219,666; 3,231,587; 3,245,910; 3,254,025; 3,271,310; 3,272,743; 3,272,746; 3,278,550; 3,288,714; 3,306,907; 3,307,928; 3,312,619; 3,341,542; 3,346,354; 3,367,943; 3,373,111; 3,374,174; 3,381,022; 3,394,179; 3,454,607; 3,346,354; 3,470,098; 3,630,902; 3,652,616; 3,755,169; 3,868,330; 3,912,764; 4,234,435; With 4,368,133; GB944,136; 1,085,903; 1,162,436; With 1,440,219; CA956,397.These patents are herein incorporated by bibliography.

As above-mentioned patent is disclosed, there is certain methods to can be used to prepare the carboxylic acid that these alkyl replace.Generally, these methods relate to handle (1) in about 100-300 ℃ temperature range, a kind of ethylenically unsaturated carboxylic acids, and carboxylic acid halides, the reactant of acid anhydrides or ester reacts with undersaturated hydrocarbon of (2) a kind of olefinic or hydrochloric ether.

When preparing the carboxylic acid of alkyl replacement, the carboxylic acid reaction thing is usually corresponding to general formula R _O-(COOH) _n, R wherein _OFeature be that to have at least one olefinic undersaturated carbon carbon covalent linkage ， And and n value be by 1 to about 6,1 or 2 integer preferably.Acid reactant also can be corresponding carboxylic acid carboxylic acid halides, acid anhydrides or ester.Usually, the sum of carbon atom should not surpass approximately 20 in the acid reactant, and preferably this numerical value is no more than approximately 10, generally should not surpass about 6.Preferably acid reactant should have the α of at least one olefinic bonds at it corresponding at least one carboxyl functional group, the β position.Acid reactant as an example has vinylformic acid, methacrylic acid, toxilic acid, maleic anhydride, fumaric acid, methylene-succinic acid, itaconic anhydride, citraconic acid, citraconic anhydride, methylfumaric acid, propene dicarboxylic acid, chloromaleic acid, equisetic acid, Ba Dousuan, methylcrotonic acid, Sorbic Acid etc.Comprise vinylformic acid, methacrylic acid, toxilic acid and maleic anhydride through preferred acid reactant.

The ethylenically unsaturated hydrocarbons reactant and the hydrochloric ether reactant that are used to prepare the carboxylic acid that these alkyl replace can be saturated basically petroleum cuts and saturated basically olefin polymer and corresponding chlorinated product.It is preferred containing 2 monoolefine deutero-superpolymer and chlorinated high polymers to about 30 carbon atoms.Useful especially superpolymer is by 1-monoolefine such as ethene, propylene, 1-butylene, iso-butylene, 1-hexene, 1-octene, 2-methyl isophthalic acid-heptene, 3-cyclohexyl-1-butylene and the 2-methyl-5-propyl group-formed superpolymer of 1-hexene.Middle alkene, promptly those olefinic bonds are not that the superpolymer at the alkene of end group position is useful equally.The example of these alkene has 2-butylene, 3-amylene and 4-octene.

The 1-monoolefine, such as narrate above those, but take place each other copolymerization or with the alkene of other copolymerization such as fragrant alkene, the multipolymer of formation such as cyclic olefin and polyene hydrocarbon also is the useful source of ethylenic unsaturated reactant.This analog copolymer comprises, for example those are by iso-butylene and vinylbenzene, iso-butylene and divinyl, propylene and isoprene, propylene and iso-butylene, ethene and piperylene, iso-butylene and chloroprene, iso-butylene and p-methylstyrene, 1-hexene and 1, the 3-hexadiene, 1-octene and 1-hexene, 1-heptene and 1-amylene, 3-methyl-1-butene and 1-octene, 3,3-dimethyl-1-amylene and 1-hexene, iso-butylene and vinylbenzene and piperylene etc. carry out polymerization and the multipolymer that makes.

Consider oily solubility, the multipolymer that being used for of wishing to want prepares the carboxylic acid that alkyl replaces preferably is aliphatic basically and is saturated basically, that is, they should calculate based on weight and contain about at least 80%, preferably about 90% unit derived from fatty monoene.Preferably, they should contain based on no more than about 5% the ethylene linkage of carbon-carbon bond sum calculating that exists.

In a specific embodiments of the present invention, superpolymer and chlorinated high polymers are by under the condition of Lewis acid catalyst such as aluminum chloride or boron trifluoride existence, it is about 35% to about 75% that butene content is calculated by weight in polymerization, and iso-butylene content is about 30% to about 60% C ₄Rectifying part makes.The iso-butylene that these polyisobutene preferably mainly comprise following configuration heavily cover unit (promptly greater than gross weight cover unit 80%):

The chlorinated hydrocarbon and the ethylenically unsaturated hydrocarbons class that are used to prepare the carboxylic acid that alkyl replaces can have high to 10,000 or even higher Mn value, though the molecular weight of the carboxylic acid through preferably having higher molecular weight is at most about 5,000, preferred about at the most 4,000, preferred about at the most 3000.The carboxylic acid that useful alkyl replaces is the carboxylic acid of the Mn value about at least 280 that has of those alkyl, and is preferably about at least 420, is more preferably approximately at least 560, is more preferably about at least 700.

The carboxylic acid that alkyl replaces also can prepare by following method, promptly carrying out halogenation such as above-mentioned olefin polymer to produce a kind of many halogenated products, these many halogenated products is converted into many nitriles and then the hydrolysis of many nitriles.Their also available potassium permanganate, nitric acid or similar oxygenant oxidation polyvalent alcohol prepare.Another method is the 2-amylene-1,3 that makes such as losing 1K by citric acid with a kind of undersaturated polycarboxylic acid, and the 5-tricarboxylic acid reacts such as the chloro polyisobutene with the hydrocarbon of a kind of alkene or polar substitution.

Monocarboxylic acid can be by using the potassium permanganate oxidation monohydroxy-alcohol, or halogenated high molecular weight olefin and ketenes reacted make.The monocarboxylic method easily of another preparation is acetylacetic ester or the malonic ester reaction of sodium Metal 99.5 with alcohol, to form the sodio-derivative of ester, again the wax of sodio-derivative and halogenated high-molecular-weight hydrocarbons such as bromination or the polyisobutene of bromination are reacted.

Monocarboxylic acid and polycarboxylic acid also can be according to United States Patent (USP)s 3,340, the method of being narrated in 281, make by the polyolefine of chlorating monobasic and polycarboxylic acid, acid anhydrides, carboxylic acid halides etc. and hydrocarbon such as those polyolefine narrated previously and the replacement of ethylenically unsaturated hydrocarbons or the unsaturated replacement of olefinic is reacted, this patent is herein incorporated as the reference data.

The acid anhydrides of monocarboxylic acid and polycarboxylic acid can make with corresponding acid dehydration.Dehydration reaction is preferably by under the dewatering agent condition that for example aceticanhydride exists, acid be heated to about more than 70 ℃ temperature and easily finish.Polycarboxylic acid such as Succinic Acid that the cyclic acid anhydrides is normally separated by no more than three carbon atoms by its carboxyl or pentanedioic acid make, linear anhydride then normally by its carboxyl by four or make more than the polycarboxylic acid that four carbon atom separates.

The carboxylic acid halides of monocarboxylic acid and polycarboxylic acid can be by acid or their acid anhydrides and a kind of halide reagent such as phosphorus tribromide, phosphorus pentachloride, or thionyl chloride is reacted and made.

In a specific embodiments, carboxylic acid is to have a substituent Succinic Acid or Succinic anhydried at least, the Succinic Acid of said replacement or its acid anhydrides contain substituting group and Succinic Acid base, substituting group wherein is derived from polyolefine, the feature of said acid or acid anhydrides is to exist on average about at least 0.9 Succinic Acid base with respect to every normal substituting group in its structure, preferably whenever the amount substituting group has about 0.9 to about 2.5 Succinic Acid bases.Polyolefinic Mn value preferably about at least 700, be more preferably about 700 to about 2000, being more preferably about 900 can be about 1 to about 10 to the ratio (being Mw/ Mn) of about 1800 weight average molecular weights (Mn) and Mn value, or about 1.5 to about 5 scope.In a specific embodiments, polyolefinic Mw/ Mn value approximately is 2.5 to about 5.Be purpose of the present invention, substituent equivalents is considered to corresponding to deriving substituent polyolefinic Mn value divided by the merchant who is present in the substituent gross weight gained in the replaced succinate.Like this; if a kind of feature of replaced succinate is substituent gross weight is 40; 000; and derive this substituent polyolefinic Mn value is 2; 000; then being characterized as of the Succinic Acid acylating reagent of this replacement always has 20(40,000/2,000=20) normal substituting group.Substituting group can be derived from one or more polyolefine, the latter is optional from containing the 2 end group alkene to the homopolymerization and the copolymerization of about 20 carbon atoms, and condition is the superpolymer unit derived from the inside alkene that contains 20 carbon atoms at the most that said multipolymer alternatively contains as many as about 25%.These are polybutene preferably, polybutene, ethylene-propylene copolymer, polypropylene, or two or more mixtures of above-mentioned polymer formation arbitrarily.In this class, also comprise those superpolymer, wherein derived from having about 50% in the total polymerization unit of polybutene at least derived from iso-butylene derived from polybutene.

In a specific embodiments, carboxylic acid is to have a substituent Succinic Acid or Succinic anhydried at least, the Succinic Acid of said replacement or its acid anhydrides contain substituting group and Succinic Acid base, substituting group wherein is derived from polybutene, wherein derived from have at least in the total polymerization unit of polybutene about 50% be derived from this polybutene of iso-butylene be characterized as the Mn value for about 1500 to about 2000, Mw/ Mn value is approximately being characterized as in their structure of 3 to about 4 these carboxylic acids or acid anhydrides and on average has about 1.5 to about 2.5 Succinic Acid bases for each normal substituting group.

In a specific embodiments, carboxylic acid is Succinic Acid or the Succinic anhydried that has a replacement at least, the Succinic Acid of said replacement or its acid anhydrides contain substituting group and Succinic Acid base, substituting group wherein is derived from polybutene, wherein derived from having at least about 50% to be derived from iso-butylene in the total polymerization unit of polybutene.This polybutene has about 800 to about 1200 Mn value, and about 2 to about 3 Mw/ Mn value.Being characterized as in their structure of this acid or acid anhydrides on average has about 0.9 to about 1.2 Succinic Acid bases for each normal substituting group.

The useful carboxylic acid of one class is the lactone of following formula representative:

R wherein ¹, R ², R ³, R ⁴, R ⁵And R ⁶Can be H independently or contain 1 alkyl that condition is that the sum of carbon atom should be abundant, so that lactone is dissolvable in water in the reaction medium (A) (II) to about 30 carbon atoms; R ²And R ³Can link together and form fat or aromatic nucleus; The α value is a zero number to about 4 scopes.In this class lactone, be useful especially by represented a kind of of following formula:

R wherein ⁷And R ⁸Be to contain 1 aliphatic group to about 30 carbon atoms, a and b are zero numbers to 5 scopes, condition be a and b and be no more than 5, c is zero a number to 4 scopes, and the experimental arrangement that the anti-And of answering of intramolecular ringization follows the elimination of water to prepare this type lactone takes place the carboxylic acid by hydroxyl is well-known in this specialty.Generally, cyclization can be promoted that reaction is to be undertaken by mixture heating up is removed the volatile matter that comprises water to the Wen Du And that raises like this such as reflux temperature such as this class material of aceticanhydride.

The useful carboxylic acid of one class is an aromatic carboxylic acid, and these sour available following formulas are represented:

Wherein R is one and preferably contains about 4 aliphatic groups to about 400 carbon atoms, and a is zero numbers to about 4 scopes, and Ar is an aromatic group, X ¹And X ²Can be sulphur or oxygen independently, b is one 1 number to about 4 scopes, condition be the adduction value of a and b be no more than Ar unsatisfied valence mumber preferably R and a select like this, make R can provide on average about at least 8 fatty carbon atom aryl perfume base Ar to have and following title identical structure of any one aromatic base for discussing in " functional group's substituted aromatics (A) (I) is (d) ".The example of useful here aromatic group comprises the multivalence aromatic base derived from compounds such as benzene, naphthalene, anthracene, phenanthrene, indenes, fluorenes, biphenyl.Generally, aromatic base used herein is to examine such as phenylene and naphthylidene, for example methylphenylene derived from the multivalence of benzene and naphthalene, the oxyethyl group phenylene, nitro phenylene, sec.-propyl phenylene, the hydroxyl phenylene, sulfydryl phenylene, N, N-diethylin phenylene, chloro phenylene, dipropoxy naphthylidene, the triethyl naphthylidene, and theirs is similar three, four, pentavalent nuclear etc.These aromatic groups can contain the substituting group of non-hydrocarbons, for example, such as various substituting groups as lower alkoxy, the low alkyl group sulfydryl, nitro, halogen is less than the alkyl and the thiazolinyl of 4 carbon atoms, hydroxyl, sulfydryl etc.The R examples of groups comprises butyl, isobutyl-, amyl group, octyl group, nonyl, 12 carbon alkyl, n-docosane base, tetracontane base, 5-chlorine hexyl, 4-oxyethyl group amyl group 4-hexenyl, 3-cyclohexyl octyl group, the 4-(rubigan)-and octyl group, 2,3,5-trimethylammonium heptyl, 4-ethyl-5-Methyl Octyl, and derived from olefin polymerization such as sovprene, polyethylene, polypropylene, polyisobutene, ethylene propylene copolymer, chlorinated alkenes superpolymer, the substituting group of the ethylene-propylene copolymer of oxidation etc.

The useful carboxylic acid of one class is those carboxylic acids with following formula:

R wherein, Ar, X ¹, X ², identical in the definition of a and b and the formula I, X ³Be oxygen or sulphur, C is 1 to about 4,1 a number to about 2 scopes normally, and condition is a, the summation of b and c is no more than the unsatisfied valence mumber of Ar, belongs to the carboxylic acid that having of this class has following formula:

Wherein R is one and preferably contains by about 4 aliphatic groups to about 400 carbon atoms.A is zero to about 4,1 a number to about 3 scopes preferably, and b is 1 to about 4,1 a number to about 2 scopes preferably, c is 1 to about 4, and preferably 1 a number to about 2 scopes is more preferably 1, and condition is a, and the summation of b and c is no more than 6.Preferably, R and a select like this, make to contain on average about at least 12 fatty carbon atoms in the aliphatic hydrocarbon substituting group with respect to each carboxylic acid molecules in the carboxylic acid molecules.Also can use the salicylic acid that aliphatic hydrocarbon replaces, wherein each aliphatic hydrocarbon substituting group contains in average about at least 8 the carbon atom ， And of each substituting group and each molecule 1 to 3 substituting group.Salt by this class Whitfield's ointment preparation, aliphatic hydrocarbon substituting group wherein is derived from olefin polymerization, the rudimentary 1-alkene of polymeric particularly, such as polyethylene, polypropylene, polyisobutene, And such as ethylene/propene copolymer and have about 30 to the average carbon content of about 400 carbon atoms is useful especially.Aromatic carboxylic acid corresponding to following formula is that well-known ， And can prepare according to this professional known experimental arrangement.Carboxylic acid pattern that these general formulas are illustrated and their neutrality of preparation and the method for alkaline metal salt are well-known, and And exists, and for example United States Patent (USP) 2,197,832; 2,197,835; 2,252,662; 2,252,664; 2,714,092; Be disclosed in 3,410,798 and 3,595,791, these patents are herein incorporated by bibliography.

The acid of sulfur-bearing (A) (I) is (b):

The acid of sulfur-bearing comprises sulfonic acid, thionamic acid, thiosulfonic acid,-sulfinic acid, sulfenic acid, and sulfuric acid, sulfurous acid and the thiosulfuric acid of partly esterification.Generally they are the salt of carbocyclic ring or fatty sulfonic acid.

Carbocyclic ring sulfonic acid comprises monokaryon and polynuclear aromatic and ring-shaped fat compound.Sulfonate, it must be dissolved in the reaction medium (A) (II), and major part can be by the following formula representative:

（R ¹a-T-（SO ₃） _b） _cM _d

Or

（R ²-（SO ₃） _b） _cM _d

In following formula, T is cyclic nuclear, such as, for example benzene, naphthalene, anthracene, phenanthrene, diphenylene-oxide, thia anthrene, phenothioxin, dibenzothiophene, thiodiphenylamine, phenyl ether, diphenyl sulfide, pentanoic, hexanaphthene, petroleum naphtha, naphthane, pentamethylene etc.; R ¹Be a fatty group such as alkyl, thiazolinyl, alkoxyl group, alkoxyalkyl, carbalkoxy etc.; A is 1 at least, R ¹ _a+ T comprises sum and is at least about 15 carbon atoms.R ²It is an aliphatic group that contains at least 15 carbon atoms.R ²Example alkyl, thiazolinyl, alkoxyalkyl, carbalkoxy etc. are arranged.R ²Specific embodiments have derived from vaseline, saturated and undersaturated paraffin and polyolefine, comprise polymeric C ₂, C ₃, C ₄, C ₅, C ₆Deng group, alkene comprises by about 15 to 7000 or more carbon atom.Group T in the following formula, R ¹And R ²Also can comprise other the inorganic or organic substituent except that above-named, such as, hydroxyl for example, sulfydryl, halogen, nitro, amino, nitroso-group, sulfide, disulphide etc.M is a hydrogen or a metallic cation (for example basic metal or alkaline-earth metal), and a, b, c and d are 1 separately at least.

In a specific embodiments, the acid of sulfur-bearing is the compound of following formula representative:

Wherein: R and R ⁴Can contain 1 independently to about 10 carbon atoms, preferably 1 alkylidene group to about 4 carbon atoms; R ¹And R ⁵Can be to contain 1 independently to about 10 carbon atoms, preferably 1 alkylidene group to about 4 carbon atoms; R ²Be one and contain 2 to about 10 carbon atoms, preferably 2 to about 4 carbon atoms, are more preferably the alkylidene group of 2 or 3 carbon atoms; R ³Be hydrogen or an alkyl, preferably hydrogen or a low alkyl group; X is O, S or NR ⁶, R wherein ⁶Be hydrogen or an alkyl, preferably hydrogen or a low alkyl group; And and n and m can be zero to about 50 or 1 to about 20 independently, or 1 a number to about 10 scopes.

Following oil-soluble sulfonic acid is useful: mahogany acid; Bright stock sulfonic acid; Derived from the Saybolt viscosity at 100 is about 100 seconds, is the sulfonic acid of about 200 seconds lube cut to Saybolt viscosity under 210 °; Sulfonic acid and many sulfonic acid that single wax and many ceruls replace, benzene for example, naphthalene, phenol, phenyl ether, naphthyl disulfide thing, pentanoic, thiophene, the above-mentioned sulfonic acid of α-Lv Dainai etc.; The sulfonic acid of other replacement such as alkyl benzene sulphonate (ABS) (wherein alkyl has 8 carbon atoms at least), hexadecyl phenol-sulfide sulfonic acid, two hexadecyl thia anthrene disulfonic acid, the dilauryl beta-naphthalenesulfonic-acid, dioctyl nitro-naphthalene-monosulfonic acid, and alkyl aryl sulphonic acid such as dodecylbenzene " bottom Residual oil " sulfonic acid.

This class sulfonic acid finally is derived from introduced 1,2,3 or more a plurality of side chain C on phenyl ring by the propylene tetramer or the iso-butylene tripolymer Wan of institute Jiization And ₁₂The sulfonic acid of substituent benzene.Dodecylbenzene bottom Residual oil mainly is single and the mixture of two replacement dodecylbenzene classes.They can be used as the by product of making household detergent and obtain.The similar product that the bottom Residual oil that forms in making linear alkyl sulfonate (LAS) process obtains through alkylation also is useful when the used sulfonate of preparation the present invention.

By with, SO for example ₃Reaction is produced sulfonate by the by product of making washing composition, and skilled personnel are well-known for this specialty.Can referring to, for example, the content in the 291st page of " sulfonate " title of " the chemical industry complete works " that KirK-Othmer writes (" Encyclopedia of Chemical Technology ") second edition the 19th volume.This book is by John Wiley ﹠amp; Sons N.Y.(1969) publishes.

Other about the description of neutral and alkaline sulfonate and prepare their method can be referring to following United States Patent (USP):

2，174，110;2，174，506;2，174，508;2，193，824;2，197，800;2，202，781;2，212，786;2，213，360;2，228，598;2，233，676;2，239，974;2，263，312;2，276，090;2，276，097;2，315，514;2，319，121;2，321，022;2，333，568;2，333，788;2，335，359;2，337，552;2，346，568;2，366，027;2，374，193;2，383，319;3，312，618;3，471，403;3，488，284;3，595，790;and??3，798，012.

These patents are herein incorporated as the reference data owing to their disclosed in this respect contents.

Fatty sulfonic acid is arranged such as paraffin sulfonic acid in being also included within, undersaturated paraffin sulfonic acid, the paraffin sulfonic acid that hydroxyl replaces, six propylidene sulfonic acid, four pentylidene sulfonic acid, polyisobutylene sulphonic acid, polyisobutene wherein contains by 20 to 7,000 or more carbon atom, the paraffin sulfonic acid that chlorine replaces, nitro paraffin sulfonic acid etc.; Ring-shaped fat sulfonic acid is such as petroleum naphtha sulfonic acid, hexadecyl cyclopentyl sulfonic acid, and lauryl cyclohexyl sulfonic acid, two-(diisobutyl) cyclohexyl sulfonic acid, the cyclohexyl sulfonic acid that single or many ceruls replace etc.

About here and sulfonic acid of being narrated in the appended claims or their salt, plan here to make a general reference all that by petroleum products deutero-sulfonic acid or their salt with term " mahogany acid " or " sulfonated petro-leum ".The useful mahogany acid of one class is the sorrel mahogany acid (claiming it to be like this because the reddish-brown that they present) that obtains as a kind of by product when making oil light oil with the sulfuric acid method.

Generally, the neutrality of above-mentioned synthetic sulfonic acid and mahogany acid and basic salt are useful when practical application of the present invention.

Phosphorated acid (A) (I) is (c):

The available following formula of phosphorated acid is represented:

X wherein ¹, X ², X ³And X ⁴Can be O independently, S or NR ³, R wherein ³Be hydrogen or an alkyl, preferably hydrogen or a low alkyl group; A and b are zero or 1 independently, R ¹And R ²Be alkyl independently.These phosphorated acid comprise the acid that contains p and s.They comprise such number acid, wherein at least one X ³Or X ⁴Be sulphur, be more preferably X ³And X ⁴The two all is a sulphur, at least one X ¹Or X ²Be oxygen or sulphur, be more preferably X ¹And X ²The two all is that Yang ， And and a and b respectively are 1.The mixture of being made up of these acid also is applicable to the present invention.R ¹And R ²Be alkyl independently, they preferably do not contain the saturated Jian And of acetylene series Bu and do not contain ethylenic unsaturated bond ， And and carbochain sufficiently long usually so that compound dissolves in the reaction medium (A) (II) yet.Preferably, R ¹And R ²Be the alkyl that contains about at least 12 carbon atoms independently, better contain about at least 16 carbon atoms, better contain about at least 20 carbon atoms, in a specific embodiments, R ¹And R ²Contain as many as about 400 or about 500 carbon atoms independently.Each R ¹And R ²Can be identical with another, though the different And of they Ke Yi and any or both can be the useful R of mixture ¹And R ²Examples of groups comprises dodecyl, eicosyl, dodecenyl succinic, naphthyl, alkyl phenyl, alkyl naphthyl, phenylalkyl, naphthyl alkyl, alkyl phenyl alkyl, alkyl naphthyl alkyl etc.Useful acid comprises those following formula representatives:

R wherein ¹And R ²Definition identical with the front.

Phosphorated acid can be at least a phosphoric acid salt, phosphonate, hypophosphite or phosphine oxide.These pentavalent phosphorus derivants can be represented with following formula:

R wherein ¹, R ²And R ³Be alkyl independently.And and a, b and c are zero independently or 1. phosphorated acid can be at least a phosphite, phosphinate, phosphinates or phosphine.These three valent phosphors derivatives can be represented with following formula:

R wherein ¹, R ²And R ³Be alkyl independently, a, b and c are zero or 1 independently.R in the general formula on each ¹, R ²And R ³In altogether carbon atom number must be fully many so that this compound is dissolvable in water in the reaction medium (A) (II).Preferably, at R ¹, R ²And R ³The sum of middle carbon atom is about 8 at least, is more preferably about at least 12, is more preferably about at least 16.To R ¹, R ²And R ³In needed total carbon atom number Mu And without limits, but the actual upper limit is about 400 or about 500 carbon atoms, in a specific embodiments, the R in the general formula on each ¹, R ²And R ³They be preferably to contain 1 independently, or 1 to about 50 carbon atoms to about 100 carbon atoms, or 1 alkyl to about 30 carbon atoms, condition is that the sum of carbon atom is about 8 at least.Each R ¹, R ²And R ³Can be identical with another, though they also can be inequality.Useful R ¹, R ²And R ³Example comprise the tertiary butyl, isobutyl-, amyl group, iso-octyl, decyl, dodecyl, petrosilane base, pentenyl, dodecenyl succinic, phenyl, naphthyl, alkyl phenyl, alkyl naphthyl, phenylalkyl, naphthyl alkyl, alkyl phenyl alkyl, alkyl naphthyl alkyl etc.

Functional group's substituted aromatics (A) (I) is (d):

By the organic materials (A) (I) of high alkalization can be at least a following formula representative functional group's substituted aromatics (A) (I) (d)

R _a-Ar-（XH） _b

Wherein R is one and preferably contains about 4 aliphatic groups to about 400 carbon atoms; Ar is an aromatic base; X is O, S, CH ₂O or CH ₂NR ¹Be that hydrogen or one preferably contain 1 to about 30 carbon atoms, be more preferably 1, be more preferably 1 alkyl (preferably alkyl or alkenyl) to about 10 carbon atoms to about 20 carbon atoms; A and b are at least 1 number independently, a and b and be in the scope of 2 numbers of replaceable hydrogen on aromatic proton or on the nuclear of Ar.Preferably, a and b are 1 to about 4 independently, are more preferably 1 number to about 2 scopes.R and a preferably select like this, abundant fatty carbon atom number are promptly arranged, so that this compound dissolves in the reaction medium (A) (II) in the R group.Preferably, the R group provides on average about at least 8 fatty carbon atoms, is more preferably about at least 12 carbon atoms.

X is that O ， And and functional group's substituted aromatics (A) (I) are phenol (d) in a specific embodiments.But, should understand aromatic base Ar And and not be only limited to benzene, as to be discussed below for this class phenol.

The R base is the alkyl that directly is connected on the aromatic base Ar.R preferably contains about 6 to about 80 carbon atoms, is more preferably about 6 to about 30 carbon atoms, be more preferably about 8 to about 25 carbon atom ， And and best be about 8 to about 15 carbon atoms.The example of R base comprises butyl, isobutyl-, amyl group, octyl group, nonyl, dodecyl, the n-docosane base, tetracontane base, 5-chlorine hexyl, 4-oxyethyl group amyl group, 4-hexenyl, 3-cyclohexyl octyl group, the 4-(rubigan) octyl group, 2,3,5-trimethylammonium heptyl, 4-ethyl-5-Methyl Octyl, and derived from polymeric alkene such as sovprene, polyethylene, polypropylene, polyisobutene, ethylene-propylene copolymer, chlorinated alkenes superpolymer, the chlorating ethylene propylene copolymer, the substituting group of the propylene tetramer and three (iso-butylene) etc.

Alkyl R is connected on the aryl Ar and can the well-known technology of these professional those of skill in the art finishes by some.Specially suitable technology is the Friedel-Crdft reaction, and wherein a kind of alkene (superpolymer that for example contains olefinic bonds), or the analogue of their halogenated or hydrohalogenation and a kind of phenol react.Reaction is to take place under the condition of Lewis acid catalyst (for example the complex compound of boron trifluoride and it and ether and phenols, hydrogen fluoride, aluminum chloride, aluminum bromide, zinc dichloride etc.) existence.The method and the condition of carrying out this reaction are well-known to these professional those skilled in the art.Can referring to, for example, roll up the 894-895 page or leaf at " chemical industry complete works " (" Encyclopedia of Chemical Technology ") second edition the 1st that Kirk-Othmer writes, in the discussion of title for carrying out in " alkylation of phenol " literary composition, this book is by the branch of John Wiley and Company, Interscience Publishers publishes, New York, 1963.Other is same suitable and easily alkyl is connected to technology on the aromatic base Ar, and skilled personnel also should be conspicuous to those these specialties.

General formula above checking can find out that these compounds contain at least one as the sort of R base defined above, and at least one functional group XH.Each above-mentioned R base all must be connected on the carbon atom as the some of an aromatic proton in the Ar base.But they needn't be connected on the same aromatic nucleus, if exist more than an aromatic proton in the Ar base.

Should understand in top general formula and this patent invention book and the appended claim everywhere, can be monokaryon with the aromatic base of Ar representative, such as phenyl, pyridyl, thienyl etc., also can be multinuclear.The multinuclear aryl can condense type, and one of them aromatic proton is fused on another nuclear at 2, such as naphthyl, and anthryl, azepine naphthyl etc.The multinuclear aryl also can be a connecting-type, and wherein having two nuclears (can be monokaryon or multinuclear) at least is that form by mutual bridging connects.These bridging units can be selected from carbon-carbon single bond, and ether connects, and ketone connects, the sulfide connection, and the polysulfide that comprises 2 to 6 sulphur atoms connects, and sulfinyl connects, and sulfone connects, and alkylidene group connects, and (annotation of translation: alkylene, alkylidene group refers to the connection of carbon alkylidene group

CH ₂

N, n are generally greater than 1; Alkylidene, alkylidene group, refer to CH=, here add that " same carbon " is to show difference), low-grade alkylidene ether connects, and alkylidene group ketone connects, low-grade alkylidene sulphur connects, the low-grade alkylidene polysulfide that contains 2 to 6 sulphur atoms connects, the amino connection, the mixing pattern of polyamino connection and this class divalence bridging.In some cases, exist in the Ar base more than the bridging chain link between a kind of two aromatic protons; For example both two benzene nucleus in fluorenes nuclear link together by a methylene radical and covalent linkage.Endorse and be considered to contain three nuclears, but wherein have only two to be aromaticity for such one.But in general, Ar will only contain carbon atom (adding the alkyl or the alkoxy substituent of any existence) in its aromatic proton itself.

Condense type, connecting-type, perhaps the two is present in the number among the Ar together, plays effect aspect the integer numerical value of a and b in decision formula XII.For example, when Ar only contains an aromatic proton, a and b's and be then by 2 to 6.When Ar contains two aromatic protons, a and μ's and be by 2 to 10.To the Ar that contain three virtue nuclears partly, a and b's and be by 2 to 15.The restriction of the value of a and b adduction is the sum that it can not surpass replaceable hydrogen on several aromatic protons among the Ar or the aromatic proton.

The monocycle aromatic proton that can be used as the Ar base can be represented with following general formula:

Wherein ar represents a monocycle aromatic proton (for example benzene) that contains 4 to 10 carbon atoms, and each Q represents a low alkyl group independently, lower alkoxy, and nitro or halogen atom ， And and m are 0 to 4.Halogen atom comprises fluorine, chlorine, bromine and iodine atom; Usually, halogen atom is fluorine and chlorine atom.

Specific embodiments when Ar is the monocycle aromatic base comprises following:

Me represent methylidene in the formula, Et represents ethyl, and Pr is a propyl group, and Nit is a nitro.

When Ar is a multinuclear condensed ring aromatic base, its available following general formula representative:

Ar wherein, the definition of Q and m is with preceding identical, m ¹Value is 1 to 4,

Represent a pair of key that condenses that condenses two rings, it makes two carbon atoms become some on the ring of per two adjacent ring simultaneously.Specific embodiments when Ar is the condensed ring aromatic base comprises following:

When aromatic base Ar was the polynuclear aromatic base of connecting-type, its available following general formula was represented:

Wherein W is 1 to about 20 integer, ar as mentioned above, condition is to have two unsatisfied (being free) valencys in all ar bases at least, the definition of Q and m is a bridged group that is selected from following group respectively with preceding identical And and each Lng, comprises carbon-carbon single bond, and ether (for example-O-) connects, ketone (for example connects

Sulfide connect (for example ,-S-), the polysulfide that contains 2 to 6 sulphur atoms connect (for example ,-S

), the sulfinyl connection (for example ,-S(O)-), the sulfone connection (for example ,-S(O ₂)-), low-grade alkylidene (for example, connects

Deng), the connection of two (low alkyl group)-methylene radical (for example ,-CR ₂-), low-grade alkylidene ether (for example, connects

-CH ₂O-，-CH ₂O-CH ₂-，-CH ₂-CH ₂-O-，

Deng), low-grade alkylidene sulfide connects (for example one or more-O-is replaced by-S-atom in low-grade alkylidene ether connects), the low-grade alkylidene polysulfide connect (for example wherein one or more-O-quilt-S

Group is replaced), amino (for example the connection

Alkyl wherein is a low-grade alkylidene etc.), polyamino (for example connects

Wherein unsatisfied free N valency should be by H atom or R Group is occupied), and mixed form (each R of connecing of this class bridging Be a low alkyl group).One or more ar bases in the aromatic group of above-mentioned connecting-type also can be by the nuclear of the type of condensing such as ar

Ar

Replace.When Ar is that the specific embodiments of connecting-type polynuclear aromatic base comprises:

Usually, except that R and-the O-group (and any bridged group) all Ar bases all be unsubstituted.Consider cost, being easy to get property, factors such as performance, the Ar base is a benzene nucleus normally, the benzene nucleus of low-grade alkylidene bridging, or a naphthalene nuclear.

In a specific embodiments, be at least a phenols of being represented by following formula by the organic materials of high alkalinityization:

Wherein: R is one and contains about 4 alkyl to about 400 carbon atoms; R ¹Be a low alkyl group, lower alkoxy, amino, amino methyl, sulfydryl, amide group, thioamides base, nitro or halogen group; A is 1 a number to about 3 scopes, and b is 1 or 2; C is 0 or 1.Usually R is one and is in-contraposition of OH base derived from having by the 2 group ， And to the monoolefine of about 20 carbon atoms of homopolymerization or copolymerization.The specific embodiments of substituent R has and approximately contains 60 polypropylene-bases to about 340 carbon atoms, approximately contain 110 poly-(ethylene/propene) bases (etc. mole of monomer ratio) to about 200 carbon atoms, approximately contain 70 poly-(iso-butylene) bases, and approximately contain 400 poly-(1-hexene/1-octene/1-decene) bases (etc. mole of monomer ratio) to about 700 carbon atoms to about 320 carbon atoms.

Source through preferred R base is a polybutene, particularly poly-(iso-butylene), they can be approximately 20 to about 70 weight percentage by total butene content, and iso-butylene content is approximately 15 C to about 60 weight percentage more specifically ₄Rectifying part is carried out polymerization and is made under the condition that a kind of Lewis acid catalyst such as aluminum chloride or boron trifluoride exist.Other component in the fraction can comprise such as ethene, propylene, divinyl and their saturated analogue and C ₄Typical other material in rectifying part.These polybutene mainly contain (greater than gross weight cover unit 80%) iso-butylene with following configuration heavily covers unit:

Active methylene compound (A) (I) is (e):

In preparation high alkalinity product (A), be used as (e) by the active methylene compound of the organic materials of high alkalinityization (A) (I), it is characterized by on a saturated carbon atom and (for example exist some unsaturated functional groups, nitro, carbonyl, cyano group, sulfone, phenyl etc.), make any hydrogen atom that is bonded on this carbon atom become comparison tart hydrogen.In a specific embodiments.The active methylene compound of wanting here to use can be represented with following formula:

Wherein: G is C(X) R, COOR, CN, R ³C=NR ⁴, CXN(R) ₂, S(O) R, SO ₂R, R ³C=CR ⁴R ⁵, C ₆H ₅Or NO ₂, wherein X is O or S, R, R ³, R ⁴And R ⁵Be hydrogen or alkyl ， And independently and work as R ³And R ⁴They can link together and form a cyclic group when being alkyl;

R ¹And R ²Be H independently, alkyl G ， And and work as R ¹And R ²They can link together and form a cyclic group when being alkyl.

The sum of carbon atom must be abundant in the compound, so that this compound is dissolvable in water in the reaction medium (A) (II).Preferably the sum of carbon atom is at least about 8 carbon atoms, be more preferably about at least 12 carbon atoms, be more preferably about at least 16 carbon atoms, the number of needed carbon atom do not had the upper limit, though be limited to about 700 carbon atoms or about 500 carbon atoms on actual.

The example of active methylene compound comprises phenylpropiophenone, methyl phenyl ketone, indenes, isopropyl tert-butyl ketone, ditane, tritane, etheric acid monooctyl ester, etheric acid 12 carbon alkyl esters and etheric acid hexadecane base ester.

The organic compound (A) (I) that replaces with the functional group of sulphur coupling (f)

By the organic materials (A) (I) of high alkalization can be the organic compound that at least a functional group that represented by following formula and the sulphur coupling replaces:

（Ⅱ）

R wherein ¹, R ², R ³And R ⁴Be H or alkyl independently of one another;

R ¹And/or R ³Can be G ¹, or G ²;

R ¹And R ²And/or R ³And R ⁴Can be to contain about 4 alkylidene groups to about 7 carbon atoms together;

G ¹And G ²Be C(X independently of one another) R, COOR, C ≡ N, R ⁵-C=NR ⁶, CON(R) ₂, or NO ₂, G ¹Can be CH ₂OH; Wherein X is O or S, each R and R ⁵Can be H or an alkyl independently, R ⁶Be H or an alkyl;

Work as G ¹And G ²The two all is R ⁵C=NR ⁶The time, these two R ⁶Group can be the alkylene that connects two nitrogen-atoms together;

Work as G ¹Be CH ₂O And and G ²When being COOR, pass through G ¹And G ²The intramolecularly combination reaction can form lactone;

X is by an integer of 1 to about 8.

R in the formula II ¹, R ², R ³And R ⁴Can be hydrogen or alkyl independently of one another.The sum of carbon atom must be abundant so that this compound is dissolvable in water in the reaction medium (A) (II).Preferably at R ¹, R ², R ³And R ⁴In the total number of carbon atoms be about at least 8, be more preferably and be at least needed carbonatoms, though the actual upper limit is about 500 or about 700 carbon atoms.Alkyl can be fat or aromatic group such as alkyl, cycloalkyl, alkylaryl, arylalkyl or aryl.R ¹And R ²And/or R ³And R ⁴Can be to contain by about 4 alkylidene groups to about 7 carbon atoms together.In these specific embodiments, R ¹And R ²And in the formula II key R that ins succession ¹And R ²Carbon atom can form a cycloalkyl together.Similarly, R ³And R ⁴And the key R that ins succession ³And R ⁴Carbon atom can form a cycloalkyl together, simultaneously, R ¹And/or R ³Also can be G ¹Or G ²

Alkyl R ¹, R ², R ³And R ⁴Specific embodiments comprise methyl, ethyl, sec.-propyl, isobutyl-, second butyl, cyclohexyl, cyclopentyl, octyl group, 12 carbon alkyl, octadecyl, the petrosilane base, n-docosane base, three decane bases, phenyl, naphthyl, styroyl, octyl phenyl, tolyl, xylyl, two (octadecyl)-phenyl, triethyl phenyl, chloro-phenyl-, p-methoxy-phenyl, dibromo phenyl, nitrophenyl, 3-chlorine hexyl etc.

The compound of formula II representative can be thia aldehyde or thia ketone.Be the G in the formula II ¹And G ²Be C(O) the R base.It is known that many kinds of thia dialdehyde compounds are arranged, and And and this compounds synthetic at prior art such as United States Patent (USP) 3,296,137 and 2,580 narrated in 695.Thia aldehyde and thia ketone most convenient ground preparation method carry out vulcanization reaction to the suitable aldehydes or ketones with following structural formula:

R wherein ¹Be hydrogen, alkyl or C(O) R, R ²Be hydrogen or an alkyl, R is hydrogen or an alkyl, in these examples, and the R in the formula II ³And R ⁴Will be separately and R ¹And R ²Identical ， And and G ¹And G ²The two all is C(O) the R base.Work as R ¹Be C(O) during R, formula II product includes 4 C(O) the R base.

Vulcanization reaction can pass through aldehydes or ketones and halogenation sulphur such as sulfur monochloride (that is S, ₂Cl ₂), sulfur dichloride, sulfur monobromide, dibrominated sulphur, and the mixture of the sulphur powder of halogenation sulphur and different quantities reacts and realizes.

The reaction of aldehydes or ketones and halogenation sulphur can mix two kinds of reactants simply and realize under required temperature, temperature range can be by approximately-30 ℃ to about 250 ℃ or higher.Through preferred temperature of reaction generally be by about 10 ℃ to about 80 ℃ scope.Reaction can be at a kind of thinner or solvent such as benzene, petroleum naphtha, and hexane, tetracol phenixin, chloroform carries out under the condition that the mineral wet goods exists.Diluent/solvent becomes easily the control of temperature of reaction, and reactant is mixed fully equably.

Aldehydes or ketones can change in wide range with respect to the consumption of halogenation sulphur.In most of the cases, reaction is to react with two moles of aldehydes or ketones and one mole of halogenation sulphur.In other cases, any in the reactant all can excessively use.When containing more than two sulphur atoms in wishing sulfide (for example X is the integer by 3-8), these compounds can make by the mixture of aldehyde and halogenation sulphur and sulphur is reacted.G ¹And G ²Different sulfur products can be by sulfuration aldehyde and ketone mixture or contain different C(O) mixture of the ketone of R group makes.

The specific embodiments of thia aldehyde and thia ketone comprises the compound of formula I representative, G wherein ¹And G ²Be C(O) the R base, the X value is 1 to 4, R ¹, R ², R ³, R ⁴As follows with R:

R ¹R ²R ³R ⁴ R

C ₂₅H C ₂H ₅H H

C ₂H ₅C ₄H ₁₁C ₂H ₅C ₄H ₁₁H

The thia aldehyde of available method for preparing and thia ketone can be converted into contain other usually can be by the derivative of their deutero-functional groups.For example, in specific embodiments more of the present invention, a kind of thia aldehyde or thia ketone can transform simultaneously that the aldehydes or ketones base becomes other end group and a kind of derivative of being converted into it with chemical reactant and/or reagent.In such reaction, thia base (Sx) and R ¹-R ⁴Group is that inertia De And remains unchanged in compound.For example, the thia dialdehyde can be converted into hydroxy-acid derivative, one of them aldehyde radical (G ¹) be converted into the COOH base, and another aldehyde radical (G ²) then be converted into CH ₂The OH base.This hydroxy-acid derivative can pass through with a kind of alkaline reagents such as a kind of alkali metal hydroxide or alkaline earth metal hydroxides on most convenient ground, preferably its content is about 5% dilute aqueous soln that forms in water to these oxyhydroxide of about 50% weight percentage, handles corresponding thia dialdehyde and makes.This class alkaline reagents can be a sodium hydroxide, potassium hydroxide, lithium hydroxide, hydrated barta, calcium hydroxide, strontium hydroxide etc.By carrying out acidifying with all example hydrochloric acids of mineral acid, the alcohol acid of can from reaction mixture, isolating out.The hydroxy-acid derivative of thia dialdehyde can be represented with following formula III:

R wherein ¹, R ², R ³, R ⁴With the definition of X with preceding identical.The specific embodiments of this class hydroxy-acid derivative comprises 6-hydroxyl-2,2-diethyl-5-propyl group-5-butyl-3,4-dithia caproic acid; 6-hydroxyl-2,2,5,5-tetraethyl--3,4-dithia caproic acid; Deng.

By means of the hydroxyl and the carboxyl that exist in the described alcohol acid of top formula III, many other can be used as can be by being converted into such hydroxyl and/or carboxyl usually and can being made by they deutero-polar groups by the organic materials of high alkalinityization.The example of this analog derivative comprise by in esterified hydroxy groups and the carboxyl any one or the two formed ester class of esterification all; By the acid amides that carboxyl forms, imines and carboxylic acid halides; Intramolecular cyclization anti-Ying And by alcohol acid is accompanied by the lactone that the elimination of water forms.The experimental arrangement for preparing this analog derivative is well-known to these professional those skilled in the art, believes needn't comprise the most description of translating of this class experimental arrangement and prolong this explanation book inadequately.More specifically, the carboxyl in the formula III can be converted into ester group (COOR) and amide group (CON(R) ₂), wherein the R base can be hydrogen or contain by 1 to 30 carbon atom, is more typically by 1 alkyl to about 10 carbon atoms.The specific embodiments of R group comprises ethyl, propyl group, butyl, phenyl etc.

The intramolecular cyclization reaction of the alcohol acid by having the formula III is accompanied by the experimental arrangement that elimination of water prepares lactone, is well-known in this specialty.Generally, cyclization can be owing to being promoted such as the existence of this class material of aceticanhydride, and reaction simultaneously can be by being heated to reaction mixture the temperature that raises like this such as reflux temperature, removes the volatile matter that comprises water simultaneously and realize.

The compound that the formula II is described, G wherein ¹And/or G ²Be R ⁵C=NR ⁶, can prepare by corresponding thia aldehyde and thia ketone.These single imines or diimine compounds can pass through one mole of dialdehyde (C(O) H) or diketone (C(O) R ⁵) react with one and two mole of amine separately and make.Amine can be monoamine or polyamine.When polyamine and thia aldehyde or thia ketone (C(O) R ⁵) when reacting, may form the cyclic diimine.For example, the G in the formula II ¹And G ²The two all is R ⁵C=NR ⁶The time, two R ⁶Base can be the alkylene that is connecting two nitrogen-atoms together.The amine that forms imines with thia aldehyde and thia reactive ketone can be described with following formula:

R ⁶NH ₂

R wherein ⁶Be hydrogen or alkyl or hydrocarbyl amino.Generally, should contain about 30 carbon atoms of as many as in the alkyl, more commonly one contains 1 aliphatic group to about 30 carbon atoms.

In a specific embodiments, the alkylamine that is used for preparing imine derivative is to contain in alkyl by about 2 to about 30 carbon atoms, is more preferably and contains in alkyl by the about 4 one-level alkyl amines to about 20 carbon atoms.Alkyl can be saturated or unsaturated.The representational example of the saturated amine of one-level be low-grade alkylamine such as methylamine, ethamine, Tri N-Propyl Amine, n-Butyl Amine 99, n-amylamine, normal hexyl Amine; And those are called as aliphatics one-level aliphatic amide and trade name is the amine of " Armeen " primary amine (product of Chicago, Illinois State Armak chemical company).Typical aliphatic amide comprises alkylamine such as normal hexyl Amine, n-octyl amine, n-Decylamine, positive 12 carbon alkylamines, n-tetradecane base amine, n-pentadecane base amine, hexadecane base amine, octodecane base amine (stearic amine) etc.These Armeen primary amines are divided into the distillation level and technical grade is sold.Amine with distillation level can obtain more purified reaction product, can form required acid amides and imines but react also with the amine of technical grade.Is Armeen-C such as those by the trade name that Armak company produces with blended fat amine, Armeen-O, and Armeen-OL, Armeen-T, Armeen-HT, Armeen S and Armeen SD etc. also is suitable for.

In a specific embodiments, amine salt is that those are derived from three grades of fatty alkyl primary amines that contain about at least 4 carbon atoms in its alkyl.For great majority wherein, they are that sum derived from carbon atom in its alkyl is less than about 30 alkyl amine.

Generally, three grades of monoamines that the fatty alkyl primary amine is the following formula representative:

Wherein R is one and contains 1 alkyl to about 30 carbon atoms.This class amine can be used TERTIARY BUTYL AMINE, uncle's hexyl primary amine, 1-methyl isophthalic acid-aminocyclohexane, uncle's octyl group primary amine, uncle's decyl primary amine, uncle's 12 carbon alkyl primary amines, uncle's n-tetradecane base primary amine, uncle's hexadecane base primary amine, uncle's octadecyl primary amine, uncle's tetracosa carbon alkyl primary amine, uncle's Octacosane base primary amine is illustrated.

The also mixture of available amine.This class amine mixt of property has " Primene 81R " as an illustration, and it is C ₁₁-C ₁₄Tertiary alkyl primary amine and " Primene JM-T ", it is C ₁₈-C ₂₂The similar mixture of tertiary alkyl primary amine (the two all can be provided by Rohm and Haas company).Tertiary alkyl primary amine and their preparation method are well-known to the general those skilled in the art of this specialty, therefore need not further discussion.Be used for the tertiary alkyl primary amine of the object of the invention and their preparation method at United States Patent (USP) 2,945, be described in 749, because this patent material in this respect has been used as bibliography and has been herein incorporated.

The primary amine that the alkyl carbochain contains ethylenic unsaturated bond also is useful.R for example ⁶Group can contain one or more ethylenic unsaturated bonds according to carbon chain lengths, the no more than two key of normally per 10 carbon atoms.Representational this class amine has dodecenyl succinic amine, tetradecene base amine, cetene base amine, vaccenic acid base amine (oil base amine) and inferior oil base amine.The unsaturated amine of this class also can have been bought by this trade name of Armeen.

Thia aldehyde and thia ketone also can react with polyamine.Useful polyamine mainly comprises one or dialkyl group, symmetrical or asymmetric quadrol, this class diamine of propylene diamine (1,2 or 1,3), and above-mentioned polyamine analogue.Suitable commodity fat polyamine has:

" Duomeen-C " (N-coconut palm fat-based-1,3-diaminopropanes),

" Duomeen S " (N-soybean oil base-1,3-diaminopropanes),

" Duomeen T " (N-tallow base-1,3-diaminopropanes) or

" Duomeen O " (N-olein base-1,3-diaminopropanes).

" Duomeen " is the binary amine that can buy from market, and it is described among the product manual NO.7-10R1 of Armak chemical company in Chicago, Illinois State.

Thia aldehyde (and ketone) carries out with available well-known technology of professional those of skill in the art of reaction of primary amine or polyamine.Generally, the thia aldehydes or ketones is in a kind of varsol, in the temperature that raises, generally reacts with amine or polyamine under nitrogen protection.When reaction was carried out, the water of formation can be with removing such as this generic operation of distillation.

The formula II is described, wherein G ¹And G ²Be COOR, C=N and NO ₂Compound, can be by having the compound of following structural formula:

R wherein ¹And R ²Definition with preceding identical, G is COOR, C=N or NO ₂, or the mixture of the different compound formation of formula IV representative, the mixture that forms with halogenation sulphur or halogenation sulphur and sulphur reacts and makes.Generally, be to react with the compound that about one mole of halogenation sulphur and about 2 moles of formula IV are represented.In a specific embodiments, R ¹Also can be G.In this case, and will contain 4 G groups in the formed sulphur compound of halogenation reaction of Salmon-Saxl, and depend on used raw material, these G groups can be identical or different.For example, when a kind of diketone such as 2, during the reaction of 4-diacetylmethane and sulfur monochloride, contain 4 ketone groups in the product that obtains; Contain a ketone group and an ester group (for example methyl aceto acetate) in raw material, the product that then obtains contains two ketone groups and two ester groups; In raw material, contain two ester groups (for example, diethyl malonate), just contain 4 ester groups in the product.By selecting the various raw materials that contain needed functional group, introduce the combination of other functional group in the sulphur compound of formula II representative in the past.

The sulfide of formula II representative, G wherein ¹And/or G ²Be the C=N base, but the compound of through type IV representative, and G wherein is C=N And and R ¹And R ²Be that hydrogen or alkyl react and make.Preferably, R ¹Be hydrogen, R ²Be an alkyl, the example of useful raw material comprises, propionitrile for example, butyronitrile etc.

G ¹And G ²Be NO ₂The formula II compound of base can pass through (1), nitro-hydrocarbon R ¹R ²C(H) NO ₂React to form the salt of nitro-hydrocarbon with a kind of basic metal or alkaline-earth metal alkyl oxide, (2) make with the sulfur monochloride reaction above-mentioned salt in a kind of inert water-free non-hydroxyl medium to form two (1-nitro alkyl) disulphide.Preferably nitro-hydrocarbon is a kind of one-level nitro-hydrocarbon (R ¹Be hydrogen, R ²Be alkyl).

The raw material primary nitro-compounds that is used for carrying out this reaction is well-known.Illustrative compound has nitroethane, 1-nitropropane, 1-nitrobutane, 1-nitro-4-methyl hexane, (2-nitro-ethyl) benzene etc.

The character that is used for making the alkanol of the basic metal of initial primary nitro-compounds or alkaline earth salt is not critical.As long as it be suitable for metal reaction to form alkoxide.Because they obtain easily and are cheap, thus low-grade alkane alcohol (alkanol that promptly contains 1 to 4 carbon atom) such as methyl alcohol, ethanol and butanols will generally be used to this synthetic in.

Salt and S ₂Cl ₂The medium of reaction must all be an inert to two kinds of reactants, medium be the And of no water and be non-hydroxyl for successfully forming new pair of (1-nitro alkyl) disulphide, also be very crucial.The example of suitable medium has ether, hexane, benzene ， diox, higher alkyl oxide etc.

Generally, in the process of preparation metal-salt preferably holding temperature between approximately 0-10 ℃.But in this step of method, temperature all still is passable by about 0 to 25 ℃.Temperature can preferably, be between about 0 to 5 ℃ in used temperature of this step of method in-5 to+15 ℃ scope when the preparation bis disulfide.

The method of the two nitro-compounds of thia for preparing the representative of various formula II is more at large by United States Patent (USP) 3,479,413 descriptions, and the content of this patent disclosure is herein incorporated by bibliography.The representational example of useful Nitrosulfide has: two (1-nitro-2-styroyl) disulphide, two (1-nitro decyl) disulphide, two (1-nitro 12 carbon alkyl) disulphide, two (1-nitro-2-phenyl decyl) disulphide, two (1-nitro-2-cyclohexyl ethyl) disulphide, two (1-nitro pentadecane base) disulphide, two (1-nitro-3-cyclobutyl propyl group) disulphide, two (1-nitro-2-naphthalene ethyl) disulphide, two (1-nitro-3-p-methylphenyl propyl group) disulphide, two (1-nitro-2-ring octyl group ethyl) disulphide etc.

The above-mentioned sulphur compound that contains carboxylicesters (is G ¹Be COOR) can be used to prepare the sulphur compound of other formula II representative.For example, ester (COOR) can be hydrolyzed to carboxylic acid (COOH), and it be by can being converted into other ester with various pure reactions, or with various amines, comprise what ammonia and one-level or secondary amine were represented by following formula such as those:

（R） ₂NH

Wherein each R is hydrogen or an alkyl, reacts and changes into acid amides, and the alkyl in the following formula can contain by 1 to about 30 carbon atoms, is more typically and contains by about 1 to 10 carbon atom.

As mentioned above, R ¹And R ²With and/or R ³And R ⁴Can be to contain by about 4 alkylidene groups to about 7 carbon atoms together.In this specific embodiment, R ¹And R ²(and R ³And R ⁴) (R simultaneously promptly ins succession in the formula II with shared carbon atom ¹And R ²That carbon atom) form a ring compound.The derivative of this class formula II can react by a saturated cyclic compound that suitably replaces and halogenation sulphur as mentioned above and make.The example of this class ring-type starting raw material comprises hexanaphthene formaldehyde (C ₆H ₁₁CHO), hexanaphthene formonitrile HCN (C ₆H ₁₁CN), cyclohexane carboxamide (C ₆H ₁₁CONH ₂), naphthenic acid (C ₆H ₁₁COOH), cyclobutane formate (C ₄H ₇COOH), suberane formic acid (C ₇H ₁₃COOH), suberyl nitrile compound (C ₇H ₁₃CN) etc.

Reaction medium (A) (II)

The reaction medium (A) (II) that is used for preparing high alkalinity product (A) is a kind of for being organic solvent inert/thinner substantially by the organic materials of high alkalinityization (A) (I).Example comprises and contains about 5 alkanes and halo alkanes to about 18 carbon atoms, the many halogen or all halogenated hydrocarbons that contain about 6 carbon atoms of as many as, the cycloalkane that contains about 5 or more carbon atoms, corresponding alkyl and/or halo cycloalkane, aryl hydro carbons, alkylaryl hydro carbons, the halogenated aryl hydro carbons, ethers is such as dialkyl ether, alkyl aryl ether, cycloalkyl ethers, cycloakyl alkyl ethers, alkanol, aklylene glycol, multi alkylidene diol, the alkyl ether of aklylene glycol and multi alkylidene diol, binary alkanoic acid diester, silicon ester, and the mixture of above these solvents.Specific embodiment comprises sherwood oil, Stoddard's solvent, pentane, hexane, octane, octane-iso, hendecane, n-tetradecane, pentamethylene, hexanaphthene, normenthane, 1, the 4-dimethyl cyclohexane, cyclooctane, benzene, toluene, dimethylbenzene, ethylbenzene, tert.-butylbenzene, halogeno-benzene such as-chlorine and polystream comprise chlorobenzene itself and 3, the 4-toluene dichloride, mineral oil, positive propyl ether, isopropyl ether, ethyl isobutyl ether, n-amylether, methyl n-amylether, cyclohexyl ether, oxyethyl group hexanaphthene, anisole, isopropoxy benzene, to methoxy toluene, methyl alcohol, ethanol, propyl alcohol, Virahol, hexanol, n-Octanol, nonylcarbinol, aklylene glycol such as ethylene glycol and propylene glycol, metacetone, butyrone, methyl butyl ketone, methyl phenyl ketone, 1,2-difluoro tetrachloroethane, dichlorofluoromethane, 1, the 2-dibromotetrafluoroethane, trichlorofluoromethane, 1-chloropentane, 1,3-dichloro hexane, methane amide, dimethyl formamide, ethanamide, N,N-DIMETHYLACETAMIDE, diethyl acetamide, propionic acid amide, diisooctyl azelate, polyoxyethylene glycol, polypropylene glycol, six-2-ethyl butoxy sily oxide etc.

Low-molecular-weight liquid polybutadiene homopolymer generally is categorized as oligopolymer, and it comprises dimer, the tetramer, and pentamers etc. also can be used as reaction medium.The illustrative example of this big class material has, the propylene tetramer for example, such liquid such as iso-butylene dimer.

From being easy to get property, the viewpoint of price and performance is considered, alkyl, and cycloalkyl and aryl hydrocarbon are represented the useful reaction medium of a class.The liquid petroleum fraction is represented another kind of useful reaction medium.In these classifications, comprise benzene and alkylbenzene, naphthenic hydrocarbon and alkylating naphthenic hydrocarbon, cycloolefin and alkylating cycloolefin such as in the naphthenic base oil fraction, exist those; And alkane, such as in the paraffin-base petroleum fraction, exist those.Sherwood oil, petroleum naphtha, mineral oil, Stoddard's solvent, toluene, dimethylbenzene etc. and all be the example of source of finance that can be used as the suitable inert organic liquid of reaction medium by the mixture that they are formed.Useful especially is that those contain the medium of at least some mineral oil as the reaction medium component.

Metal base (A) (III)

The metal base that is used to prepare the high alkalinity product is to be selected from following material: basic metal, alkaline-earth metal, titanium, zirconium, molybdenum, iron, copper, zinc, aluminium, the mixture that two or more in them are formed, perhaps their alkali reaction compound.Preferably, this metal is a basic metal, alkaline-earth metal, zinc, aluminium or two or more mixtures formed in them.Lithium, sodium, potassium, magnesium, calcium, barium are useful, lithium wherein, sodium, potassium are useful especially.Sodium is particularly preferred.

The alkali reaction compound can be any compound of any above-mentioned metal or metal mixture, as long as its alkalescence is stronger than the alkalescence of the corresponding metal salt of the acidic substance that are used to prepare the high alkalinity product (A) (V).These compounds comprise alkoxide, nitrite, carboxylate salt, phosphite, sulphite, hydrosulphite, carbonate, supercarbonate, borate, oxyhydroxide, oxide compound, alkoxide, acid amides etc.Nitrite, carboxylate salt, phosphite, alkoxide, carbonate, borate, oxyhydroxide and oxide compound are useful.Oxyhydroxide wherein, oxide compound, alkoxide and carbonate are useful especially.

The example of operable metal base comprises Iron diacetate, phenylformic acid iron, iron protocarbonate, ironic formiate, iron lactate, iron protoxide, ferric oxide, ortho phosphorous acid iron, ferrous sulfite, bisulfite iron, propionic acid copper, neutralized verdigris, cupric metaborate, cupric benzoate, Tubercuprose, lauric acid copper, cupric nitrite, Palmiticacid copper, Cupric salicylate, Red copper oxide, copper carbonate, naphthoic acid copper, Zinc dibenzoate, zinc borate, zinc lactate, zinc oxide, Zinic stearas, zinc sulfite, sodium-acetate, Sodium Benzoate, sodium bicarbonate, sodium bisulfite, yellow soda ash, Trisodium Citrate, sodium hydroxide, inferior sodium phosphate, sodium metabisulfite, naphthoic acid sodium, Sodium Nitrite, S-WAT, Potassium ethanoate, potassium benzoate, saleratus, Potassium hydrogen sulfite, salt of wormwood, Tripotassium Citrate, potassium hydroxide, ortho phosphorous acid potassium, inclined to one side Potassium hydrogen sulfite, naphthoic acid potassium, potassium nitrite, penta potassium borate, S-WAT, titanium dioxide, titanium monoxide, titanous oxalate, the acetic acid zirconium, zirconium white, zirconium carbonate, zirconium hydroxide, zirconium lactate, naphthoic acid zirconium, sesquialter molybdenum oxide, molybdic oxide, molybdic acid, calcium acetate, calcium bisulfite, lime carbonate, calcium hydroxide, calcium laurate, naphthoic acid calcium, calcium nitrite, caoxalate, phosphorous acid calcium, calcium stearate, calcium sulfite, magnesium acetate, magnesium bisulfite, magnesiumcarbonate, magnesium hydroxide, Magnesium monolaurate, naphthoic acid magnesium, magnesium nitrite, magnesium oxalate, phosphorous acid magnesium, Magnesium Stearate, magnesium sulfite, strontium acetate, strontium bisulfite, Strontium carbonate powder, strontium hydroxide, lauric acid strontium, naphthoic acid strontium, strontium nitrite, strontium oxalate, phosphorous acid strontium, strontium stearate, strontium sulfite, barium acetate, barium bisulfite, barium carbonate, hydrated barta, barium laurate, naphthoic acid barium, barium nitrite, barium oxalate, phosphorous acid barium, barium stearate, barium sulfite, aluminum borate, aluminium hydroxide etc.The hydrate of above-claimed cpd also is useful.

Promotor (A) (IV)

Promotor, i.e. those permissions are incorporated excess metal into go in the high alkalinity product material, and also be Ge Yang And of Ge kind and be well-known in this specialty, as indicated in the patent documentation of quoting as proof.The acidity of these materials must acidity than the acid material that is used to prepare the high alkalinity product (A) (V) a little less than.The detailed especially discussion of relevant suitable promotor can be referring to United States Patent (USP) 2,777, and 874,2,695,910 and 2,616,904, they are herein incorporated by bibliography.These comprise alcohols and phenol accelerant, and they are through preferred.Alcohol promotor comprises contains 1 alkanol to about 12 carbon atoms.Phenol promotor comprises benzene and the naphthalene that various hydroxyls replace.A useful especially class phenol is United States Patent (USP) 2,777, the alkylating phenols of listing in 874 of a class, heptyl phenol for example, octyl phenol, nonyl phenol, 12 carbon alkylphenols, propylene tetramer phenol etc.The also mixture of available various promotor.

Useful promotor comprises water, ammonium hydroxide, and Nitromethane 99Min. contains the organic acid of 8 carbon atoms of as many as, metal chelating agent such as salicylic aldehyde oximes (alkyl (C for example ₁-C ₂₀) salicylaldoxime), and alkali metal hydroxide such as lithium hydroxide, sodium hydroxide and potassium hydroxide, and contain about 30 carbon atoms of as many as, about 20 carbon atoms of as many as preferably are more preferably the monobasic and the polyvalent alcohol of about 10 carbon atoms of as many as.The example of this class alcohol comprises methyl alcohol, ethanol, Virahol, amylalcohol, hexalin, octanol, 12 carbon alkanols, decyl alcohol, mountain alcohol (n-docosane alcohol), ethylene glycol, Diethylene Glycol, triethylene glycol, ethylene glycol monomethyl ether, trimethylene, hexamethylene glycol, glycerine, tetramethylolmethane, benzylalcohol, phenylethyl alcohol, Sorbitol Powder, nitro-propanol, chloroethanol, monoethanolamine, styryl carbinol, allyl alcohol etc.Useful especially is to contain the monohydroxy-alcohol of about 10 carbon atoms of as many as and the mixture of methyl alcohol and the formation of more senior monohydroxy-alcohol.

Acid material (A) (V)

The patent that suitable acid material has also been quoted as proof above, for example United States Patent (USP) 2,616,904, and is disclosed.In the useful acid material of a known class, comprise carboxylamine, acetic acid, formic acid, boric acid, trinitromethane, SO ₂, CO ₂, the source of said acid and their mixture.CO ₂And SO ₂And their source is a preferable material.Useful CO ₂The source comprise urea, carbaminate and volatile salt.Useful SO ₂The source comprise sulfurous acid, thiosulfuric acid and SODIUM HYDROSULPHITE.CO ₂It is particularly preferred material.

The preparation of high alkalinity product (A)

In a specific embodiments, high alkalinity product (A) is by contacting by the organic materials of high alkalinityization (A) (I) with acid material (A) (V), reaction medium (A) (II), the mixture of metal base (A) (III) and promotor (A) (IV) makes.And then chemical reaction takes place.The temperature that acid material contacts remaining reactive material depends on used promotor (A) (V) to a great extent.When using phenol accelerant, temperature range usually is by about 100 ℃ to about 200 ℃ generally at about 60 ℃ to about 300 ℃.When using alcohols or mercapto-type-accelerator, temperature generally is no more than the reflux temperature ， And of reaction mixture and preferably is no more than about 100 ℃.The precise nature of the high alkalinity product (A) that obtains is unknown.But it can suitably be described to reaction medium and (1) or a kind of by metal base for the purpose of patent specification, acid material and the metal network thing that is formed by the organic materials of high alkalinityization, (2) and/or a kind ofly react with metal base and by the organic materials of high alkalinityization and the single-phase uniform mixture of the amorphous metal salt that forms by acid material.For example, if mineral oil is used as reaction medium, mahogany acid is used as by the organic materials of high alkalinityization, Ca(OH) ₂Body is a metal base, carbonic acid gas is as acid material, the high alkalinity product (A) that then obtains can be described to or by acid material for purpose of the present invention, the oil solution of the metallic complex compound that metal base and mahogany acid form, or the oil solution of amorphous calcium carbonate and calcium mahogany sulfonate.Because high alkalinity product (A) is many known And and they only is the intermediate of the sulfuration high alkalinity product that here uses as preparation, so the accuracy of these materials is verified, and to send out And bright in this be not critical.

The high alkalinity product (A ') of boracic

In one embodiment, the high alkalinity product is the high alkalinity product (A ') of at least a boracic.They can prepare by at least a high alkalinity product (A) is contacted with at least a boron compound.Boron compound can be a boron oxide, the boron oxide hydrate, and boron trioxide, boron trifluoride, boron tribromide, boron trichloride, boric acid such as organic boronic (is an alkyl-B(OH) ₂Or aryl-B(OH) ₂), boric acid (is H ₃BO ₃), tetraboric acid (is H ₂B ₄O ₇), metaboric acid (is HBO ₂), the various ester classes of boric anhydride and this class boric acid.Use boron trihalides and ethers, organic acid, the complex compound of inorganic acids or hydro carbons are a kind of method easily in the boron reactant introducing reaction mixture.This class complex compound is known, and the example has boron trifluoride-triethyl, boron trifluoride-phosphoric acid, boron trifluoride-Mono Chloro Acetic Acid, boron tribromide-dioxs, and boron trifluoride-methyl ethyl ether.

The specific embodiments of organic boronic comprises methyl-boron-dihydroxide, phenyl-boron dihydroxide, and cyclohexyl boric acid is to heptyl benzene ylboronic acid and 12 carbon alkylboronic acidss.

Boric acid ester comprises the monoesters that particularly boric acid and following alcohols or phenols form, diester and three esters, such as, methyl alcohol for example, ethanol, Virahol, hexalin, cyclopentanol, the 1-octanol, sec-n-octyl alcohol, 12 carbon alkanols, mountain alcohol, oleyl alcohol, stearyl alcohol, benzylalcohol, 2-butyl hexalin, ethylene glycol, propylene glycol, trimethylene, 1, the 3-butyleneglycol, 2,4-hexylene glycol, 1, the 2-cyclohexanediol, 1,3-ethohexadiol, glycerine, tetramethylolmethane, Diethylene Glycol, diethylene glycol monoethyl ether, ethylene glycol monoethyl ether (cellosolve), three second diether, three propylidene glycol, phenol, naphthols, to butylphenol, the neighbour, right-diheptyl phenol, cyclohexyl phenol, 2,2-pair-(p-hydroxybenzene) propane, the phenol that polyisobutene (molecular weight about 1500) replaces, ethylene chlorhydrin, ortho chloro phenol, m-nitrophenol, 6-bromine octanol and 7-ketone-decyl alcohol.More rudimentary alcohols, 1, the 2-glycols, 1, the 3-glycols, promptly those contain this class alcohol that is less than about 8 carbon atoms, are useful especially for being prepared as the borate ester that the invention is intended to.

The method for preparing boric acid ester is known ， And open in this area (for example " Chemieal Reviews " the 56th volume 959-1064 page or leaf).A kind of method is that the alcohol of boron trichloride and 3 moles or phenol reaction are produced boric acid three organic esters.Another kind method is boron oxide and alcohol or phenol reaction.Another kind method is alcohol or the phenol direct esterification tetraboric acid and 3 moles, and also having another kind of method is boric acid and a kind of glycol direct esterification and form, for example, and a kind of cyclic boric acid alkylene ester.

High alkalinity product (A) is realized with the hybrid technology that contacts available standards of boron compound.The boron compound equivalent can reach about 40: 1 or higher to the normal ratio of high alkalinity product (A), typically about 0.05: 1 to about 30: 1 scope, usually be at about 0.2: 1 to about 20: 1 scope.Often the equivalent ratio of using is about 0.5: 1 to about 5: 1, and preferably about 0.5: 1 to about 2: 1, more frequent was about 1: 1.Be purpose of the present invention, the equivalent of boron compound is based on the mole number of boron in the said compound.For example, the equivalent of boric acid equals its molar weight, the equivalent of tetraboric acid then be it molar weight 1/4th.The equivalent of high alkalinity product (A) is based on the equivalents of metal in the said high alkalinity product that can be used to react with boron.The equivalent of metal is based on its valence mumber.For example, one mole of monovalence metal such as sodium provides the monovalent metal, and needs two mole of two valency metal such as calcium just can provide monovalent such metal.This numerical value available standards technology (for example make indicator with bromine phenol etc. and measure total basicnumber by titration) is measured.For example, a kind of monovalent that contains can be used to high alkalinity product (A) with the metal of boron reaction, and its equivalent equals its actual weight.Can be used to high alkalinity product (A) with the metal of boron reaction and contain two equivalents, its equivalent is half of its actual weight.

Temperature can be had in the scope of minimum decomposition temperature to the decomposition temperature of reactant or required product by room temperature, preferably at about 20 ℃ to about 200 ℃, be more preferably about 20 ℃ to about 150 ℃, be more preferably about 50 ℃ to about 150 ℃, be more preferably about 80 ℃ to about 120 ℃.

Be the time that need be used for forming the metal borate (for example Sodium Tetraborate) of desired concn in the high alkalinity product (A ') of boracic duration of contact.This concentration available standards technology (is for example measured dissolved solid concentration, is measured the water that forms in the reaction by the boration method, measure by metathetical acidic substance (A) (V), for example CO in the high alkalinity product (A) when boron compound is solid ₂Deng) measure.Generally, be by about 0.5 to about 50 hours duration of contact, usually is by about 1 to about 25 hours, preferably about 1 to about 15 hours, is more preferably about 4 to about 12 hours.

Following example A-1 to A-45 has illustrated the preparation of high alkalinity product (A) or (A ').Unless specialize, in all examples and in the whole patent specification and in the appended claim, umber and percentage number average by weight, all temperature are centigradetemperature.

Example A-1

Preparation is by 853 gram methyl alcohol, 410 gram tempered oils, 54 gram sodium hydroxide and be the required formed mixture of sodium hydroxide of neutralization in addition.The acid number of the sulfonic acid that added after the amount of the sodium hydroxide of Jia Ruing depended on afterwards.The temperature regulation to 49 of mixture ℃, add the mixture of 1070 gram straight chain dialkyl benzene sulfonic acids (molecular weight=430) and tempered oil (active ingredient accounts for 42% weight percentage), the while, holding temperature was at 49-57 ℃.Add the Succinic anhydried that 145 gram polyisobutene (digital average molecular weight=950) replace, add 838 gram sodium hydroxide again.Temperature regulation to 71 ℃, in reaction mixture, be blown into 460 gram carbonic acid gas.Mixture rapid evaporation to 149 ℃, filter and make transparently, promptly get required product.Product is overbasic sodium sulfonate, has base number (indicator such as bromine phenol) 440, metal content 19.45% weight percentage, and metal is than 20, vitriol the ash content of coal 58% weight percentage, sulphur content 1.35% weight percentage.

Example A-2

160 gram tempered oils, a kind of product of the Succinic anhydried that 111 gram polyisobutene (digital average molecular weight=950) replace, 52 gram propyl carbinols, 11 gram water, 1.98 gram Peladow(Dow Chemical companies is accredited as the CaCl that contains 94-97% ₂) and the mixtures that form of 90 gram white limes mix.Add the sulfonic acid that white lime added afterwards with neutralization in addition.The amount of the said white lime that this adds in addition depends on the acid number of sulfonic acid.(active ingredient content is that 42% weight percentage) And makes the temperature of reaction mixture be no more than 79 ℃ to the oil solution of adding 1078 gram straight chain dialkyl benzene sulfonic acids (molecular weight=430).Temperature regulation to 60 ℃, add 64.5 gram heptyl phenol, the product of lime and formaldehyde reaction and 217 gram methyl alcohol.It is 20-30 that reaction mixture purges up to base number (tetrabromophenol sulfonphthalein indicator) with carbonic acid gas, in reaction mixture, add 112 gram white limes, mixture with carbonic acid gas purge to base number (phenolphthalein indicator) be 45-60, the temperature of keeping reaction mixture simultaneously is at 46-52 ℃.One step of back is added white lime then heavily cover three times with the operation that carbonic acid gas purges again, reaction mixture is 45-55 by carbonatization up to base number (phenolphthalein indicator) when just heavily covering the last time.Reaction mixture 93-104 ℃ of flash drying, is used the pan drying at 149-160 ℃, filter the back and be adjusted on the level of 12.0% calcium contents with oil.Product is a kind of overbasic calcium sulphonate, and it has total basicnumber (tetrabromophenol sulfonphthalein indicator) 300, metal content 12% weight percentage, and metal is than 12, vitriol the ash content of coal 40.7% weight percentage, sulphur content 1.5% weight percentage.

Example A-3

Preparation mainly is the mixture ， And that forms of Succinic anhydrieds that fork chain monoalkylated benzenes sulfonic acid (molecular weight=500), 771 gram o-Xylols, 75.2 gram polyisobutene (digital average molecular weight=950) replace temperature regulation to 46 ℃ by 1000 grams.Add 87.3 gram magnesium oxide, adding 35.8 gram acetic acid add 31.4 gram methyl alcohol and 59 gram water, restrain carbonic acid gas at 49-54 ℃ of purging reaction mixture with 77.3.Add 87.3 gram magnesium oxide, 31.4 gram methyl alcohol and 59 gram water restrain carbonic acid gas at 49-54 ℃ of purging reaction mixture with 77.3 again, above-mentioned adding magnesium oxide, and the first alcohol and water, then the step that purges with carbonic acid gas is heavily covered once again.By under atmospheric pressure with the decompression under rapid evaporation o-Xylol, the first alcohol and water is removed from reaction mixture, reaction mixture is filtered to clarification by cold but And.Product is a kind of overbasic sulfonic acid magnesium, and it has base number (tetrabromophenol sulfonphthalein indicator) 400, metal content 9.3% weight percentage, and metal is than 14.7, vitriol the ash content of coal 46.0%, sulphur content 1.6% weight percentage.

Example A-4

At room temperature, the mixture that preparation is formed by 790 gram alkylated benzenes sulfonic acid, 71 gram polybutylene-based Succinic anhydrieds (equivalent about 560) and 176 gram mineral oil in reactor.In this mixture, add sodium hydroxide (320 gram), then add 640 gram methyl alcohol.Because this reaction mixture heat release, the temperature of the mixture that obtains rose to 89 ℃ (backflows) in 10 minutes.In the meantime, reaction mixture with carbonic acid gas with the 4Cfh(cubic feet/hour) the speed carbonatization.Continue about 30 minutes of carbonatization, at this moment the temperature of reaction mixture is reduced to 74 ℃ gradually.Methyl alcohol and other volatile matter evaporates from the mixture of carbonatization remove by be blown into nitrogen with the speed of 2Cfh in mixture in about 90 minutes, the while slowly is warming up to 150 ℃.After evaporation is finished reaction mixture was kept in 155-165 ℃ temperature range about 30 minutes, filter the oil solution that promptly obtains required alkaline sulfoacid sodium then, the metal that it has is than about 7.75.

Example A-5

Preparation restrains methanol mixed to it and 800 gram sodium hydroxide and 704 by 780 gram alkyl benzene sulphonate (ABS)s, 119 gram polybutylene-based Succinic anhydrieds (equivalent about 560) and the formed mixture of 442 gram mineral oil.Reaction mixture contacts 11 minutes with the flow velocity of 7cfh with carbonic acid gas at first, and at this moment temperature slowly rises to 97 ℃.The flow velocity of carbonic acid gas is reduced to the temperature of 6cfh And and mixture and in about 40 minutes, slowly reduce to 88 ℃.Again the carbon-dioxide flow prompt drop is contacted about 35 minutes to 5cfh, temperature of reaction is slowly reduced to 73 ℃ simultaneously.Be blown into nitrogen 105 minutes by speed in the mixture of carbonatization, simultaneously temperature slowly risen to 160 ℃ of evaporations and remove volatile matter with 2cfh.After evaporation is finished, the temperature of mixture at 160 ℃ kept other 45 minutes again, filter the oil solution that promptly produces required alkaline sulfoacid sodium then, the metal ratio that it has is approximately 19.75.

Example A-6

The mixture ， And that preparation is made up of the alkylating Phenylsulfonic acid of 3120 grams, 284 gram polybutylene-based Succinic anhydrieds (equivalent about 560) and 704 gram mineral oil restrains methanol mixed to it and 1280 gram sodium hydroxide and 2560.The carbonic acid gas that this reaction mixture flow velocity is 10cfh carried out carbonatization about 65 minutes altogether.During this period of time the temperature of reaction mixture rises to 90 ℃ and slowly is reduced to 70 ℃ then.The nitrogen purging 2 hours that with flow velocity is 2cfh is to evaporate volatile matter, and the temperature of mixture is increased to 160 ℃ at leisure simultaneously.After evaporation is finished, mixture was kept 0.5 hour at 160 ℃, filter the oil solution that promptly produces limpid required sodium sulfonate then, the metal ratio that it has is 7.75.

Example A-7

The mixture ， And that preparation is made up of 3200 gram alkyl benzene sulphonate (ABS)s, 284 gram polybutylene-based Succinic anhydrieds (equivalent about 560) and 623 gram mineral oil restrains methanol mixed to it and 1280 gram sodium hydroxide and 2560.The reaction mixture flow velocity is that the carbonic acid gas of 10cfh carried out carbonatization about 77 minutes altogether.The temperature of reaction mixture rises to 92 ℃ during this period, drops to 73 ℃ then gradually.With flow velocity is about 2 hours of the nitrogen purging of 2cfh, makes the temperature of reaction mixture slowly be increased to 160 ℃ so that volatile matter is evaporated removes simultaneously.Last trace volatile matter can make it to evaporate from reaction mixture with the vacuum of 30mm/Hg and 170 ℃ temperature.After evaporation was finished, mixture kept under 170 ℃ temperature, filtered the limpid oil solution promptly produce required sodium sulfonate then, and it has about 7.72 metal ratio.

Example A-8

The mixture And that preparation is made up of the alkylating Phenylsulfonic acid of 780 grams, 86 gram polybutylene-based Succinic anhydrieds (equivalent about 560) and 254 gram mineral oil restrains methanol mixed to it and 480 gram sodium hydroxide and 640, the reaction mixture flow velocity is that the carbonic acid gas of 6cfh carried out carbonatization about 45 minutes altogether, the temperature of reaction mixture rises to 95 ℃ during this period, is cooled to 74 ℃ then gradually.With the nitrogen purging of flow velocity 2cfh about 1 hour, the temperature that makes reaction mixture simultaneously by 74 ℃ rise to 160 ℃ so that volatile matter by evaporating in the reaction mixture.After evaporation is finished mixture was kept other 0.5 hour at 160 ℃, filtered the oil solution that promptly produces required high alkaline azochlorosulfonate acid sodium then, its metal ratio is 11.8.

Example A-9

The mixture And that preparation is made up of the alkylating Phenylsulfonic acid of 3120 grams, 344 gram polybutylene-based Succinic anhydrieds (equivalent about 560) and 1016 gram mineral oil restrains methanol mixed to it and 1920 gram sodium hydroxide and 2560, the mixture flow velocity is that the carbonic acid gas of 10cfh carried out carbonatization in about 2 hours, during this carbonatization, the temperature of mixture is increased to 96 ℃, is cooled to 74 ℃ then at leisure.By being the nitrogen purging 2 hours of 2cfh with flow velocity, make temperature be increased to 160 ℃ with indirect heating simultaneously by 74 ℃, volatile matter is evaporated from reaction mixture.Mixture after evaporation filters then other 1 hour of 160 ℃ of heating, and filtrate is carried out vacuum-evaporation (30mm/Hg) to remove small amount of water at 160 ℃, filters the solution that promptly provides required high alkaline azochlorosulfonate acid sodium once more, and its metal ratio is about 11.8.

Example A-10

The mixture ， And that preparation is made up of the alkylating Phenylsulfonic acid of 2800 grams, 302 gram polybutylene-based Succinic anhydrieds (equivalent about 560) and 818 gram mineral oil restrains methanol mixed to it and 1680 gram sodium hydroxide and 2240.The reaction mixture flow velocity is that the carbonic acid gas of 10cfh carried out carbonatization about 90 minutes altogether.During this carbonatization, the temperature of reaction mixture rises to 96 ℃, is cooled to 76 ℃ then at leisure.With flow velocity be 2cfh Dan air-blowing Sao And by indirect heating make temperature by 76 ℃ rise to 165 ℃ so that volatile matter by being evaporated in the reaction mixture.By 35mm/Hg(at 165 ℃) vacuum-evaporation remove water in the reaction mixture.Promptly obtain the solution of required overbasic sodium sulfonate after the filtration.The metal ratio is about 10.8.

Example A-11

Prepare one by the alkylating Phenylsulfonic acid of 780 grams, the mixture ， And that 103 gram polybutylene-based Succinic anhydrieds (equivalent about 560) and 350 gram mineral oil are formed restrains methanol mixed to it and 640 gram sodium hydroxide and 640.The reaction mixture flow velocity is that the carbonic acid gas of 6cfh carried out carbonatization about 1 hour.During this carbonatization, the temperature of mixture rises to 95 ℃, is cooled to 75 ℃ then gradually.With flow velocity be 2cfh about 95 minutes of nitrogen purging so that volatile matter by being evaporated in the reaction mixture.During this evaporation, the temperature of reaction mixture was reduced to 70 ℃ at first in 30 minutes, rose to 78 ℃ then in 15 minutes.Then in 80 minutes mixture heating up to 155 ℃.Mixture after evaporation at 155-160 ℃ temperature range internal heating other 30 minutes filters then, and filtrate is the oil solution of required high alkaline azochlorosulfonate acid sodium, and its metal ratio is about 15.2.

Example A-12

The mixture ， And that preparation is made up of the alkylating Phenylsulfonic acid of 2400 grams, 308 gram polybutylene-based Succinic anhydrieds (equivalent about 560) and 991 gram mineral oil restrains methanol mixed to it and 1920 gram sodium hydroxide and 1920.Reaction mixture is by being that the carbonic acid gas of 10cfh closely contacts and carried out carbonatization about 110 minutes altogether with flow velocity.During this period, the temperature of reaction mixture rises to 98 ℃ at first, reduces to 76 ℃ at leisure then in about 95 minutes.With flow velocity be the nitrogen air-blowing of 2cfh sweep And make the temperature of reaction mixture slowly rise to 165 ℃ so that the first alcohol and water from reaction mixture, be evaporated.160 ℃ of temperature, make last trace volatile matter under the condition of vacuum 30mm/Hg by steaming in the reaction mixture.After vacuum-evaporation, mixture is filtered the oil solution promptly produce required high alkaline azochlorosulfonate acid sodium, it has 15.1 metal ratio.

Example A-13

Preparation is by the alkylating Phenylsulfonic acid of 780 grams, and the mixture ， And that 119 gram polybutylene-based Succinic anhydrieds (equivalent about 560) and 442 gram mineral oil are formed restrains methanol mixed to it and 800 gram sodium hydroxide and 640.The carbonic acid gas that with flow velocity is 8cfh carried out carbonatization to mixture about 55 minutes, and during this carbonatization, the temperature of mixture rises to 95 ℃ and reduces to 67 ℃ then at leisure.With the nitrogen purging of flow velocity 2cfh about 40 minutes, make simultaneously the temperature of reaction mixture rise at leisure 160 ℃ so that the first alcohol and water from reaction mixture, steam.After the evaporation, the temperature of mixture was kept in 160-165 ℃ temperature range about 30 minutes, filtered the solution promptly provide corresponding sodium sulfonate then, and it has about 16.8 metal ratio.

Example A-14

The mixture of 836 gram petroleum sodium sulfonates in the oil solution that contains 48% oil and 63 gram polybutene Succinic anhydrieds (equivalent about 560) introduced a reactor Zhong And be heated to 60 ℃.This mixture and 280 gram sodium hydroxide and 320 gram methanol mixed.The reaction mixture flow velocity is that the carbonic acid gas of 4cfh carried out carbonatization about 45 minutes altogether.During this period.The temperature of reaction mixture rises to 85 ℃ and reduces to 74 ℃ then at leisure.With flow velocity be the nitrogen purging of 2cfh make simultaneously the temperature of mixture rise to gradually 160 ℃ so that volatile matter steam.After evaporation is finished, mixture was heated other 30 minutes at 160 ℃.Filter then and promptly produce corresponding sodium salt in solution.Product has 8.0 metal ratio.

Example A-15

1256 gram petroleum sodium sulfonates are being contained 48%(weight) oil and the mixture in the oil solution of 95 gram polybutene Succinic anhydrieds (equivalent about 560) introduce the anti-Qi of answering Zhong And and be heated to 60 ℃.With this solution and 420 gram sodium hydroxide and 960 methanol mixed.Be that the carbonic acid gas of 4cfh feeds in the mixture and can finish carbonation reaction in totally 60 minutes with the flow velocity.Temperature rises to 90 ℃ earlier during this period, and then slowly drops to 70 ℃.Feed nitrogen, slowly be warmed up to 160 ℃ simultaneously volatile matter is removed from the mixture of carbonatization.Keep reaction mixture about 30 minutes 160 the evaporation back, filters then and promptly obtain metal than the sodium sulfonate oil solution that is about 8.

Example A-16

Holding temperature in 30 minutes, toward the oil solution (the vitriol ash is 7.6%) of 3245 gram barium mahogany sulfonates, adds 73 gram barium oxide in the mixture that 32.5 gram octyl phenols and 197 gram water form between 57-84 ℃.With mixture heating up to 100 ℃ And this temperature maintenance 1 hour so that remove nearly all water.Holding temperature feeds 75 parts of carbonic acid gas in reaction mixture between 133-170 ℃ in 3 hours.The intermediate product of 1000 carbonatizations that make above of gram, the mixture heating up to 100 that 121.8 gram octyl phenols and 234 gram hydrated bartas are formed ℃ is then 150 ℃ of heating 1 hour.Flow velocity with 3cfh fed carbonic acid gas 1 hour in mixture then.Filtration is through the product of carbonatization, and the vitriol the ash content of coal of filtrate is 39.8%, and the metal ratio is 9.3.

Example A-17

Stir the barium mahogany sulfonate of 1285 grams 40% and the mixture that 500 ml methanol form at 55-60 ℃, past wherein branch adds 301 gram barium oxide in 1 hour simultaneously.Add the back and continue to stir 2 hours, handled 2 hours at 55-65 ℃ with carbonic acid gas then at 45-55 ℃.The mixture that obtains is heated to 150 ℃ and removes methyl alcohol with evaporation, and resistates filters through siliceous flocculating aids, and is limpid, and brown filtrate is sulfur-bearing hydrochlorate ash 33.2% by analysis, and the metal ratio is 4.7.

Example A-18

57 gram nonyl alcohols and 301 are restrained barytic mixture under agitation, 150-175 ℃ of heating 1 hour, be cooled to 80 ℃ then, restrain methyl alcohol toward wherein adding 400, the mixture that obtains stirred 30 minutes at 70-75 ℃, handle with the barium mahogany sulfonate of 1285 grams 40% then, mixture was stirred 1 hour at reflux temperature, fed carbonic acid gas 2 hours at 60-70 ℃ then, under the 18mmHg column pressure with mixture heating up to 160 ℃, filter then, filtrate is a limpid brown oil, and it has following analytical value: vitriol ash 32.5%, metal is than 4.7.

Example A-19

At 55 ℃, toward 1145 gram content is 40%(weight) the mineral oil solution of barium mahogany sulfonate and mixture that 100 gram methyl alcohol form in add 220 gram barium oxide, flow velocity with 2-3cfh feeds carbonic acid gas in mixture simultaneously, in this mixture, add other 78 gram methyl alcohol, and then add 460 gram barium oxide, in mixture, feed carbonic acid gas simultaneously.The product of carbonatization is heated to 150 ℃ And keeps 1 Xiao Shi And filtration, the sulfate ash content of filtrate is 53.8% weight percentage, and metal is than 8.9.

Example A-20

Is 750 gram content 60%(weight) the oil solution of petroleum sodium sulfonate and the solution that forms of 67 gram calcium chloride and 63 gram water carry out replacement(metathesis)reaction and promptly make conventional calcium mahogany sulfonate, reactant 90-100 ℃ of heating 4 hours so that petroleum sodium sulfonate is converted into calcium mahogany sulfonate.Add 54 gram lime then, mixture was 150 ℃ of heating 5 hours.Mixture is cooled to 40 ℃, adds 98 gram methyl alcohol, holding temperature fed 152 gram carbonic acid gas in 20 hours between 42-43 ℃.Reactant is heated to 150 ℃ to anhydrate and alcohol to remove.Residuum in the reaction vessel dilutes with 100 parts of low viscous mineral oil.The analytical value that the oil solution of the calcium sulphonate high alkalinity material of the desired carbonatization that obtains after filtration shows below: vitriol the ash content of coal 16.4%, metal is than 2.5.By in product, adding the oxide compound or the oxyhydroxide of barium or calcium, then carry out carbonatization again, the metal ratio can be increased to 3.5 or higher as expecting.

Example A-21

Is 880 gram content 57.5%(weight) the calcium sulphonate oil solution of three decyl benzene bottoms Residual oil (the bottom Residual oil consists of one, two, mixture with three decyl benzene), the mixtures of 149 gram methyl alcohol and 59 gram calcium hydroxides pack into the anti-Qi of answering Zhong And vigorous stirring, mixture heating up was fed carbonic acid gas 0.5 hour to 40-45 ℃ And with the flow velocity of 2cfh.Then the reaction mixture of carbonatization is heated to 150 ℃ to remove pure and mild any water that exists.For the purpose of purifying is filtered residuum.Product is the oil solution of calcium sulphonate material of the desired high alkalinity carbonatization of content 61% weight percentage, and it has following analytical value: the ash content of coal 16.8%, metal is than 2.42.At basic metal or alkaline earth metal oxide, further carbonatization can make metal be increased to 3.5 or higher than easily under the condition that oxyhydroxide or alkoxide exist.

Example A-22

Containing 1%(weight) the mixtures of oil solution of 2090 grams, 45% weight percentage calcium mahogany sulfonate of water, 74 gram calcium hydroxides and 251 gram ethylene glycol 100 ℃ of heating 1 hour, at 40-45 ℃ of feeding carbonic acid gas 5.5 hours in the reaction mixture.Mixture is heated to 185 ℃ to remove ethylene glycol and any water that exists under the 10.2mm mercury column.Filter residuum and promptly obtain desired high alkaline calcium sulfonate material, it has following analytical value: sulfated ash 12.9%, metal is than 2.0.Carrying out carbonatization in the presence of calcium oxide or calcium hydroxide can make metal bring up to 3.5 or higher like that such as expectation.

Example A-23

The high alkalinity materials of 1595 gram example A-20,167 grams as follows the one-level amylalcohols of calcium hydroxide, 288 gram methyl alcohol, 88 gram isopropylcarbinols and the 56 gram blended isomeries of phenol calcium salt, 616 gram mineral oil, 167 grams 91% of preparation (contain 65% Pentyl alcohol approximately, 3% primary isoamyl alcohol and 32% 2-methyl-1-butene alcohol) mixture 40 ℃ of vigorous stirring, holding temperature was feeding 25 gram carbonic acid gas in 2 hours between 40-45 ℃, further add calcium hydroxide subsequently three times, each add-on is 157 grams, and calcium hydroxide of every adding feeds carbonic acid gas just as the front; The carbonatization step was promptly accused and is finished after the 4th time calcium hydroxide added.Reactant 43-47 ℃ of further carbonatization 1 hour.Being neutral carbonation reaction mixture heating up to 150 ℃ substantially, be blown into nitrogen simultaneously and remove the water that produces in pure and mild any reaction with evaporation, residuum in the filtration reactor, filtrate, it is the oil solution of desired high alkaline calcium sulfonate, have following analytical value: vitriol the ash content of coal 41.11%, metal is than 12.55.

By restraining mineral oil to 2250,960 gram heptyl phenol and 50 gram water add phenol calcium salt that the anti-Qi of answering Zhong And uses on 25 ℃ of stirrings prepare, mixture heating up to 40 ℃, in 1 hour toward wherein adding 7 gram calcium hydroxides and the commercially available Paraformaldehyde 96 of 231 grams 91%.Mixture heating up to 80 ℃, holding temperature was adding other 200 gram calcium hydroxides (making total amount is 207 grams) again in 1 hour between 80-90 ℃.Mixture heating up to 150 a ℃ And is kept this temperature 12 hours, feed simultaneously nitrogen in the mixture with except that anhydrating.Filtering reaction thing then.Filtrate, promptly content is the oil solution of phenol calcium salt of the desired heptyl phenol-formaldehyde condensation products of 33.6% weight percentage, its vitriol the ash content of coal is 7.56%.

Example A-24

Is 574 gram content 40%(weight) the mixture of barium mahogany sulfonate oil solution, 98 gram furfuryl alcohols and 762 gram mineral oil 100 ℃ of heated and stirred 1 hour, in 15 minutes, add 230 gram barium oxide then in batches.The reaction later stage then heats mixture 1 hour at 150-160 ℃ because the exothermic heat of reaction temperature rises to 120 ℃.Keep this temperature then with carbon dioxide treatment 1.5 hours, reactant be heated to 150 ℃ concentrate under the 10mm mercury column, filter then a limpid oil soluble filtrate, have following analytical value: vitriol the ash content of coal 21.4%, metal is than 6.1.

Embodiment-25

At 80 ℃, in 0.75 hour toward 1614 gram polyisobutenyl succinic anhydride (is that 4.3% Chong amount Bai Fen is Shuoed chloro polyisobutene and the MALEIC ANHYDRIDE that And on average contains 67 carbon atoms and made in about 200 ℃ of reactions by the chlorine average content), 4313 gram mineral oil, add 1038 gram lithium hydroxide-hydrates in the mixture of 345 gram heptyl phenol and 200 gram water, be heated to 105 ℃ simultaneously.When the inherence was heated to 150 ℃ to reaction mixture in 1.5 hours, add 75 gram isooctyl alcohol.Holding temperature fed carbonic acid gas 3.5 hours at 150-170 ℃ And with the flow velocity of 4cfh.Through the flocculating aids filtering mixt, filtrate is desired product, and it has the vitriol the ash content of coal of 18.9% weight percentage, and metal is than 8.0.

Embodiment-26

244 gram oleic acid, begin to add 172.6 gram calcium oxide after the mixture heating up to 70 ℃ of 180 gram one-level isooctyl alcohol and 400 gram mineral oil.Mixture removed 150-160 ℃ of heating in 3 hours simultaneously anhydrates, in 1 hour, add in the mixture 324 gram hydrated barta-water close thing And by side arm water trap continuously except that anhydrating.Feed in the mixture carbonic acid gas shows faint acidity when mixture is checked with phenolphthalein till at 150-160 ℃.After carbonation reaction is finished mixture is heated to 150 ℃ to remove all remainder water and alcohol substantially at the 35mm mercury column, residuum is desired high alkalization product, and it comprises barium and two kinds of metals of calcium.

Embodiment-27

Polyisobutene (molecular-weight average 750) be equivalent to the Socl of its weight 47.5% ₂Prepared sulfoxide in 4.5 hours 220 ℃ of reactions.This sulfoxide of 787 grams, 124 gram diisobutyl phenol, the mixture of 550 gram mineral oil and 200 gram water is warming to 70 ℃ ， And and handles with 360 gram barium oxide.This mixture reflux 1 hour, And used carbon dioxide treatment at 150 ℃, (checks with phenolphthalein) till mixture is neutrality substantially.Filter then and promptly obtain a limpid oil soluble liquid, it has following analytical value: vitriol ash 22.8%; Metal is than 5.8.

Embodiment-28

At 70 ℃, toward 268 gram oleic acid, 675 gram mineral oil add 308 gram barium oxide in the mixture of 124 gram diisobutyl phenol and 146 gram water.With mixture reflux 1 hour, then at 150 ℃ toward wherein feeding carbonic acid gas, till mixture is neutrality substantially to phenolphthalein.The reactant filtration is promptly obtained limpid brown oil dissolubility filtrate, and it has following analytical value: vitriol the ash content of coal 29.8%, metal is than 6.0.

Example A-29

Prepare one by 423 gram Sperm whale oils, 124 gram heptyl phenol, the mixture that 500 gram mineral oil and 150 gram water are formed, temperature regulation to 70 ℃, add 308 gram barium oxide,, be heated to 150 ℃ and carry out dry And and maintain under the same temperature and use carbon dioxide treatment, carry out carbonatization till reactant is subacidity to phenolphthalein mixture reflux 1 hour.Filter and promptly to get not heavy-gravity high alkalinity liquid of a limpid light brown, it has following analytical value: vitriol the ash content of coal 32%, metal is than 6.5.

Example A-30

In the mixture of 174 gram N-octadecyl propylene diamines, 124 gram diisobutyl phenol, 766 gram mineral oil, 146 gram water, add 306 gram barium oxide, refluxed then 1 hour.Temperature is elevated to 150 ℃ anhydrates with basic removing; Keep this temperature, feed carbonic acid gas, when reactant is neutrality substantially (phenolphthalein check) stop to add carbonic acid gas ， And reactant filtered, promptly get one limpid, oil-soluble liquid, it has following analytical value: vitriol the ash content of coal 28.9%; Metal is than 5.8.

Example A-31

Is 6000 gram content 30%(weight) the mixture heating up to 60 ℃ of barium mahogany sulfonate oil solution (vitriol ash 7.6%), 348 gram p-tert-butylphenols and 2911 gram water.Add 1100 gram barium oxide, simultaneously temperature is elevated to 94-98 ℃.Keep this temperature about 1 hour, and in 7.5 hours, temperature slowly was elevated to 150 ℃ then.Further keep 150 ℃ 1 hour to guarantee removing all water substantially, the high alkalinity material that obtains is a brown liquid, has following analytical value: vitriol the ash content of coal 26%, metal is than 4.35.In this product, feed SO ₂, up to 327 gram SO are arranged ₂Only be combined into the high alkalinity materialization, the neutralization value of the product that obtains like this is zero.Through SO ₂The material of handling is a brown liquid.Restrain 1000 through SO ₂High alkalinity material of handling and 286 gram Shui Hun He And are heated to about 60 ℃ temperature, slowly add subsequently 107.5 gram Yangization Bei And temperature maintenance 94-98 ℃ 1 hour, then the entire reaction thing at about 1 hour internal heating to 150 ℃ And other a hour in this temperature maintenance.Filter the high alkalinity material of purifying and obtaining, filtrate is the high alkalinity material of brown liquid shape, and it has following analytical value: vitriol the ash content of coal 33.7%; Metal is than 6.3.

Example A-32

At 0-30 ℃, the molecular weight that makes with the aluminum chloride-catalyzed isobutene polymerisation be the polyisobutene of 700-800 at 70-75 ℃ with nitrated 4 hours of 10% excessive 70% aqueous nitric acid.By under 75mmHg pressure, being heated to 75 ℃ to remove the volatile components in the product mixtures.In the mixture of the so nitrated polyisobutene of 151 grams, 113 gram heptyl phenol, 155 gram water and 2057 gram mineral oil, add 612 gram barium oxide at 70 ℃.Mixture 150 ℃ of heating 1 hour, is used carbon dioxide treatment, till mixture is neutrality (phenolphthalein indicator is at 25 ℃ of experimental arrangements of pressing ASTMD-974-53T) then under same temperature.Product mixtures is filtered, and filtrate has following analytical value: vitriol the ash content of coal 27.6%, N percentage composition 0.06; Metal is than 9.

Example A-33

Being that to restrain hydroxy radical contents be the mixture heating up to 90 formed of 8.3% heptyl phenol ℃ to 44% rosin Amine D (mainly containing dehydroabietylamine) and 245 by 630 gram nitrogen contents, at 90-140 ℃ it is mixed with 230 gram barium oxide then, 140 ℃ with nitrogen purge mixture, get 600 grams partly above-mentioned reactant restrain mineral oil Xi Shi And filtration with 400.Filtrate feeds carbonic acid gas, and with the benzene dilution, reheat is removed benzene.Filter with dimethylbenzene Hun He And.Gained filtrate is 20% xylene solution of product, its barium sulfate the ash content of coal is 25.1%, and nitrogen content 2%, backflow base number are that the basicity of 119(metal composites is represented with the suitable KOH milligram number of every gram composition), for simplicity, the basicity of measuring like this is called " backflow base number ".

Example A-34

Press legal system and be equipped with the amine aldehyde condensation products: at reflux temperature, it is 100-105 ℃, divide small quantities of the adding in the mixture of being made up of 1392 gram N-octadecyl propylene diamines, 300 gram mineral oil, 200 gram water and 42 gram calcium hydroxides 420 gram formaldehyde, the rate of addition of formaldehyde should be avoided the over-drastic foaming.Mixture reflux temperature heating 1 hour, slowly is heated to 155 ℃ ， And again and purged two hours with nitrogen at 150-155 ℃, to remove all volatile components.Filter then, filtrate is content 65.4% weight percentage, and nitrogen content is the oil solution of 2.4 amine aldehyde condensation products.

It is that 90% barium monoxide Hun He And is heated to 70 ℃ that the above-mentioned filtrates of 1850 grams and 185 gram heptyl phenol, 1485 gram mineral oil and 1060 are restrained purity.Added 500 gram water in 1 hour, holding temperature is between 70-100 ℃ simultaneously.Mixture was heated 4.7 hours at 110-115 ℃, and then be warmed up to 150 ℃.Holding temperature in 140-150 ℃ the reaction mixture carbonatization, filter then.Filtrate is content 57.8% weight percentage, nitrogen content 0.87%, and the barium sulfate the ash content of coal is the oil solution of 29.5% high alkalinity amine aldehyde condensation products.

Example A-35

5846 grams (mineral oil content is 66%(weight)) the calcium sulfate the ash content of coal is the mixture heating up to 80 ℃ of oil solution, 464 gram heptyl phenol and the 3.4 gram water of 4.68% neutral calcium sulfonate.In 0.6 hour, add 1480 gram barium oxide.The temperature of exothermic heat of reaction ， And and reaction mixture reaches 100 ℃.Mixture is heated to 150 ℃ And in this temperature carbonatization.In the process of carbonatization, in mixture, add 24 gram bariumchlorides.In the operating process of carbonatization, remove in by reaction mixture and deoil.Continuing carbonatization in this temperature is 80 up to the base number (phenolphthalein indicator) of mixture.164 gram octanols and a kind of flocculating aids adding mixture Zhong And are filtered mixture while hot.Filtrate is desired high alkalinity barium sulfonate, and its barium sulfate the ash content of coal is 26.42%, and metal is than 4.6, backflow base number 104.

Example A-36

Is the mixture that 1000 polyisobutene and 90 gram thiophosphoric anhydrides form one of room temperature preparation by 1000 gram molecular weights, in 5 hours it is heated to 260 ℃ And in this temperature maintenance other 5 hours.The sour phosphorus content of the hydrolysis that obtains is 2.4% weight percentage, and sulphur content is 2.8% weight percentage.In another container, by mixing 2200 gram mineral oil and 1150 gram barium oxide at 88 ℃, And is at 150 ℃ during with this mixture 3 of water vapor purging and make the mixture of oil and hydrated barta.Holding temperature is between 145-150 ℃, and the hydrolysis acid that makes above in batches adding in this mixture in 3 hours added 360 gram heptyl phenol then in 1.5 hours.At the 150-157 ℃ of speed with 100 grams per hour feeding carbonic acid gas 3 hours in the mixture that obtains.Purge 150 ℃ temperature with nitrogen through the product of carbonatization and 850 gram Kuang things oil Hun He And and to make it drying.Product is filtered, and filtrate is 25% solution with mineral oil dilution becoming barium sulfate the ash content of coal.The phosphorus content of final solution is 0.48%, and the backflow base number is 109, and the metal ratio is 7.2.

Example A-37

(a) in the mixture of 268 gram oleyl alcohol, 124 gram heptyl phenol, 988 gram mineral oil and 160 gram water formation, add 168 gram lithium hydroxide-hydrates.Mixture then 150 ℃ of carbonatizations, basically is a neutral up to it reflux temperature heating 1 hour.This is filtered through mixture of carbonatization to obtain a Lithium Sulphate content be 12.7% liquid.

(b) at 80 ℃, in 0.75 hour toward 1614 gram polyisobutenyl succinic anhydride (be that 4.3% Chong amount Bai Fen Shuo chloro polyisobutene and MALEIC ANHYDRIDE that And on average contain 67 carbon atoms in about 200 ℃ reactions make by the chlorine average content), 4314 gram mineral oil, add 1038 gram hydrated barta-hydrates in the mixture that 345 gram heptyl phenol and 200 gram water form, be heated to 105 ℃ simultaneously.Add 75 gram isooctyl alcohol, simultaneously mixture at about 1.5 hours internal heating to 150 ℃.The temperature of keeping mixture is that the carbonic acid gas of 4cfh purged 3.5 hours with the flow velocity at 150-170 ℃ And.Reaction mixture is filtered by flocculating aids, and filtrate is desired product, and its vitriol the ash content of coal is 18.9%, and the metal ratio is 8.

Example A-38

Method by above-mentioned example A-36 prepares thiophosphoric acid.By in 1.5 hours, holding temperature is added to metal base in the mineral oil solution and heptyl phenol of this acid in 100-110 ℃, can form one by this acid of 890 grams, 2945 gram mineral oil, the formed mixture of 445 gram heptyl phenol.Then mixture 150 ℃ of dryings 2 hours, toward wherein feeding carbonic acid gas, phenolphthalein is slightly acidic with the flow velocity of 4cfh up to reaction mixture, need 3.5 hours approximately, holding temperature is in 150-160 ℃ scope at the same time.Then reaction mixture is filtered twice through diatomaceous earth filter.Filtrate is the lithium salts of required high alkalinity thiophosphoric acid, has metal than 6.3.

Example A-39

(a) 2442 gram mahogany acid strontiums, 3117 gram mineral oil, 150 gram isooctyl alcohol and 910 gram methanol mixture are heated to 55 ℃.Holding temperature added 615 gram strontium oxides in 10 minutes between 55-65 subsequently.Kept same temperature reheat after adding 1 hour, the flow velocity with 4cfh fed carbonic acid gas about 3 hours in mixture then, up to reaction mixture phenolphthalein was faint acidity.Then reaction mixture is heated to 160 ℃ ， And and kept this temperature about 1 hour, the flow velocity with 5cfh feeds nitrogen simultaneously, then product is filtered, and filtrate is desired high alkalinity material, and the metal ratio is 3.8.

(b) at 70 ℃, in 0.25 hour, be to add 1216 gram lithium hydroxide-hydrates in the mixture of mahogany acid lithium minerals oil solution (its vitriol ash is 6.27%), 460 gram heptyl phenol, 1920 gram mineral oil and 300 gram water of 50% weight percentage toward 3800 gram content, mixture was stirred 1 hour at 110 ℃, at 2.5 hours internal heating to 150 ℃, flow velocity with 4cfh fed carbonic acid gas about 3.5 hours, was neutral substantially up to reaction mixture.Mixture is filtered, and filtrate is required product, and its vitriol the ash content of coal is 25.23%, and the metal ratio is 7.2.

Example A-40

The mixture of 406 gram petroleum naphthas and 214 gram amylalcohols under agitation is heated to 38 ℃, add 27 gram barium oxide, slowly add 27 gram water then, temperature rises to 45 ℃, continue to stir, in 0.25 hour, slowly add simultaneously 73 gram oleic acid, continuing under the blended condition mixture heating up to 95 ℃.Interrupt heating, in mixture, slowly add 523 gram barium oxide.Temperature rises to about 115 ℃, allows mixture be as cold as 90 ℃, slowly adds 67 gram water in mixture, so temperature rises to 107 ℃.Then mixture 107-120 ℃ of scope internal heating 3.3 hours, simultaneously in the reactant feeding nitrogen to remove moisture content.Holding temperature added 427 gram oleic acid at 120-125 ℃ in 1.3 hours then.Ting ends Jia Re And and adds 236 gram petroleum naphthas, and holding temperature is at 108-117 ℃, simultaneously with the flow velocity of 2cfh in the reactant feeding carbonic acid gas 1.5 hours to carry out carbonation reaction.Mixture removes under nitrogen purging and anhydrates, and reaction mixture is filtered promptly get a filtrate twice, and it has following analytical value: vitriol the ash content of coal 34.42%, metal is than 3.3.

Example A-41

1800 grams are contained 21.7%(weight) mineral oil, 36.14%(weight) high alkalinity calcium mahogany sulfonate, 426 gram petroleum naphthas, 255 gram methyl alcohol and 127 gram equimolar amount isopropylcarbinols and the formed reaction mixture of amylalcohol of petroleum naphtha under refluxad be heated to 45 ℃.Add 148 gram Mississippi lime (commercially available calcium hydroxide).Flow velocity with 2cfh feeds further adding 148 gram Mississippi lime of carbonic acid gas ， And in reactant then.Keep same temperature and continue carbonatization 1 hour, in reaction mixture, append two batches 147 gram Mississippi lime again.Every interpolation is once promptly along with the carbonatization process of carrying out 1 hour.Then reactant is heated to 138 ℃, anhydrates and methyl alcohol to remove with nitrogen purging simultaneously.Obtain 2220 gram metals after the filtration than the solution that is 12.2 high alkalinity barium mahogany sulfonate.

Example A-42

The mixture that 1122 gram polyisobutene (molecular-weight average 950) Succinic anhydrieds, 1122 gram dimethylbenzene and 2000 gram mixing oils are formed under agitation is heated to 80 ℃.In 10 minutes, add 580 gram sodium hydroxide.Reaction mixture at 1.3 hours internal heating to 120 ℃.Then under refluxad reaction mixture heating 6 hours, temperature is elevated to 150 ℃ And and collects 300 ml water distillates during this period.Reaction mixture is chilled to Shi Wen And kept this temperature 16 hours.Again reaction mixture is heated to 77 ℃, adds 540 gram sodium hydroxide.In 1.7 hours, reaction mixture is heated to 140 ℃, makes and under refluxad remove 150 ml waters.In reaction mixture, feed CO ₂5 hours, azeotropic steamed 150 ml waters simultaneously.Be chilled to Shi Wen And toward reaction mixture and kept this temperature 16 hours, again reaction mixture is heated to 77 ℃, add 560 gram sodium hydroxide.In 1.7 hours, reaction mixture is heated to 140 ℃, makes and under refluxad remove 150 ml waters.In reaction mixture, feed CO ₂5 hours.Azeotropic steams 150 ml waters simultaneously.Reaction mixture Leng is but kept this temperature 16 hours to Shi Wen And, again reaction mixture is heated to 77 ℃, add 640 gram sodium hydroxide.In 1.7 hours, reaction mixture is heated to 140 ℃, makes and under refluxad remove 150 ml waters.In reaction mixture, feed CO ₂5 hours, azeotropic steamed 150 ml waters simultaneously.Reaction mixture is chilled to Shi Wen And kept this temperature 16 hours.Reaction mixture is heated to 77 ℃ again, adds 560 gram sodium hydroxide, in 1.7 hours, reaction mixture is heated to 140 ℃ and makes and under refluxad remove 150 ml waters.In reaction mixture, feed CO ₂5 hours, azeotropic steamed 150 ml waters simultaneously.Reaction mixture is chilled to Shi Wen And kept this temperature 16 hours, add 1000 gram thinning oils,, add 200 in the reaction mixture and restrain super-cells reaction mixture heating evaporation to 115 ℃ under the 30mmHg post.In 15 hours, reaction mixture is filtered with the filter of putting 80 gram flocculating aidss well.The vitriol the ash content of coal of the product that obtains is 43.4%, base number (bromine phenol etc.) 361, proportion 1.11.

Example A-43

In room temperature preparation by 794.5 kilograms of polyisobutenyl (molecular-weight average 950) Succinic anhydried, 994.3 kilograms of SC-100 solvents (Russia Russia solvent company product is a kind of aromatic hydrocarbon solvent through evaluation), 858.1 kilograms of mixing oils, 72.6 kilograms of kerosin and formed mixtures of 454 gram caustic soda sheets that tetrapropylene phenol, 154.4 kg of water, 25 ℃ of viscosity of 113.5 grams are 1000Cst Dow Corning 200.The exotherm of reaction mixture is about (unit time) 10 ℃.Reaction mixture is under refluxad in 1.5 hours internal heating to 137.8 ℃.In reaction mixture, feed CO with 45.4 kilograms speed per hour ₂5.9 hour, reaction mixture is cooled to 82.2 ℃, by the water distillate of removing 146.2 kilograms in the reaction mixture, 429 kilograms of organic distillates are added back in the reaction mixture again.Reaction mixture is heated to 138 ℃, adds 45.4 kilograms of caustic sodas, holding temperature feeds CO with 45.4 kilograms speed per hour in reaction mixture between 135-141 ℃ ₂5.9 hour, reaction mixture is heated to 149 ℃ And keeps this temperature and stop up to distillation.In 5 hours, remove 149.4 kg of water distillates and 487.6 kilograms of organic distillates.Reaction mixture is flashed to 160 ℃ under 70mmHg post absolute pressure.By removing 37.7 kg of water distillates and 500.3 kilograms of organic distillates in the reaction mixture, add 858.1 kilograms of mixing oils, 68.1 kilograms of super-cells are put into reaction mixture, filter reaction mixture promptly obtains required product.The vitriol the ash content of coal of the product that obtains is a 38.99%(weight) sodium content 12.63%(weight), CO ₂Content 12.0%(weight), the viscosity 94.8cst that base number (bromine phenol etc.) is 320,100 ℃, proportion 1.06.

Example A-44

The product that 1000 grams are made by example A-1, the anti-whipping agent of 0.13 gram (kerosins of Dow Corning 200 Fluid that 25 ℃ of viscosity is 1000 cst) and 133 restrain the mixture that mixing oils form and under agitation are heated to 74-79 ℃.Add 486 gram boric acid, reaction mixture is heated to 121 ℃ to remove water in the dereaction and the CO that is included in the 40-50% weight percentage in the example A-1 product ₂₀Reaction mixture is heated to 154-160 ℃ And to be kept this temperature and is reduced to 0.3%(weight respectively up to free and total water content) or still less reach 1-2%(weight).Reactant Leng is but arrived Shi Wen And to be filtered.

Example A-45

The product that 1000 grams are made by example A-3 and the mixture heating up to 79 of 181 gram thinning oils ℃ add 300 gram boric acid, in 8 hours reaction mixture are heated to 124 ℃.With the temperature maintenance of reaction mixture between 121-127 ℃ 2-3 hour, remain on 6.85%(weight up to Mg content) constant till.Beginning to blow with nitrogen and sweep And and reaction mixture is heated to 149 ℃ anhydrates to remove, is 3% weight percentage or still less up to the content of water.The reaction mixture filtration is promptly got required product.

Example A-46

Preparing one is the petroleum sodium sulfonate oil solution of 40% weight percentage and the formed mixture of Succinic anhydried that 99 gram polyisobutenyl (molecular-weight average is 950) replace by 68 gram tetrapropylene phenol, the neutral mixing oil of 374 grams, 100 solvents, 561 gram oil-contgs.Under agitation in mixture, add 306 gram caustic soda globules.Be under the nitrogen purging of 0.5cfh reaction mixture to be heated to 156 ℃ at flow velocity, feeding flow velocity in the mixture is the CO of 0.7cfh ₂4.5 hour.Carry out nitrogen purging to remove the water that accumulates in the dereaction with the speed of 0.5cfh simultaneously.Bathe temperature maintain 156 ℃ 0.5 hour, meanwhile carry out nitrogen purging with the speed of 0.5cfh.Reaction mixture is cooled to 50 ℃, toward wherein adding 305 gram caustic soda globules.Under agitation, carry out nitrogen purging with the speed of 0.5cfh simultaneously, with the CO of 0.6cfh speed mixture heating up to 156 ℃ ₂Fed in the reaction mixture 5 hours.The nitrogen that with speed is 0.5cfh during carrying out the carbonatization step simultaneously purges.In the temperature of following mixture vacuum-evaporation to 160 of 20mm/Hg post ℃ to remove remainder water in the dereaction.Mixture is promptly got 1343 gram products with 190 gram super-cells filtrations.Kinematic viscosity when the proportion the when total basicnumber of product is 435,15.6 ℃ is 1.258,100 ℃ is 85.09.

Above Examples set various preparations be suitable for being converted into the method for the high alkalinity product (A ') of the high alkalinity product (A) of sulfuration high alkalinity product of the present invention or boracic.Change these examples produce any required high alkalinity material all should be within this professional skilled person's limit of power.For example, (V) (SO particularly of other acidic substance (A) of narrating of those fronts ₂) be used for replaced C O in can superincumbent example ₂₀Similarly, other metal base (A) (III) also can be used for using in any example that provides the occasion of metal base.Perhaps the mixture of alkali and/or energy also can be used by the mixture of the material of high alkalization.Similarly, nonpolar as the mineral oil of high alkalization medium or reaction medium (A) (II) or other, the consumption of inert organic liquid also can change in the scope of broadness in height alkalizes reaction process and in height alkalization product.

Use SO ₂Or SO ₂The source replaces acid material (A) (V)

In a specific embodiments, the acid material that is used to prepare high alkalinity product (A) or boracic high alkalinity product (A ') is SO ₂Or a kind of SO ₂The source.And and in this specific embodiment the high alkalinity product be after its production, discuss as following, vulcanize with sulphur or sulphur source (B) and form sulfurized high alkalinity product of the present invention.But in other specific embodiments, acid material (A) (V) is not SO ₂Or SO ₂(that is, acid material is CO in the source ₂, carboxylamine, acetic acid, formic acid, boric acid, trinitromethane etc.); And and in these specific embodiments, the high alkalinity product (A ') of high alkalinity product (A) or boracic and the SO of significant quantity ₂Or a kind of SO ₂The source contacts has the long time so that replace the acid material (A) (V) of part at least carry out sulfidation with sulphur or sulphur source (B) before or in the sulfidation from the high alkalinity product.

The high alkalinity product (A ') and the SO of high alkalinity product (A) or boracic ₂Or SO ₂The solution-air contact technique (for example purge, spray etc.) of standard is preferably used in contact between the source.In a specific embodiments, SO ₂Flow velocity can be with about 0.1 to about 100cfh, preferably about 0.1 to about 20cfh, more preferably about 0.1 to about 10cfh, more preferably about 0.1 to about 5cfh.High alkalinity product and SO ₂Or SO ₂The contact in source should last till always that the acid material of requirement is by SO ₂Or SO ₂Till the source replaces.Generally, preferably use SO ₂Or SO ₂The source fully replaces acid material fully or basically.But unsubstituted acid material to the weight ratio of substituted acid material can be in 20: 1 scope of as many as ， And and can usually be about 1: 1 to about 1: 20 by about 20: 1 to about 1: 20 in some instances.Available those be known technology to this professional skilled person, such as Infrared spectroscopy, base number mensuration waits the process of assaying reaction and required terminal point.

SO ₂The source comprises the oxygen acid of sulphur.These comprise sulfurous acid, thiosulfuric acid and SODIUM HYDROSULPHITE.

The minimum decomposition temperature that temperature of reaction can have from the room temperature to the reactant or in the required product, preferably between about 70 ℃ to about 250 ℃, usefully about 100 ℃ to about 200 ℃ and about 120 ℃ to about 170 ℃ scope.

Reaction times depends on needed replacement degree.Reaction can be carried out ， And and usually be to carry out in about 18 hours about 3 in about 0.1 to about 50 hours time.

Point out as top, use SO ₂Or SO ₂The source replaces acid material and can or carry out in sulfidation before with sulphur or sulphur source (B) the high alkalinity material being vulcanized.As handle SO ₂Or SO ₂The source replaces the reaction of acid material and when with sulphur or sulphur source (B) the high alkalinity material being carried out the sulfurized reaction and carries out simultaneously, the speed of having observed required thiosulfuric acid salt formation is fast unexpectedly.

Following example A-47 to A-50 provides and has used SO ₂Or SO ₂The source replaces the indicative working method of acid material (A) (V) from the high alkalinity product.

Example A-47

At 133-135 ℃, feed 403 gram (12.6 equivalent) SO in the product that in 8 hours, obtains by example A-1 toward 1610 grams (12.6 equivalent) with the flow velocity of 0.5-2cfh ₂CO in the product that obtains ₂Contents level is a 1.47%(weight), total basicnumber (bromine phenol etc.) is 218.Sulphur content is a 12.1%(weight), sodium content is a 17.6%(weight).

Example A-48

At 140-150 ℃, feed 376 gram (11.75 equivalent) SO in the product that in 8 hours, obtains by example A-1 toward 3000 grams (23.5 equivalent) with the flow velocity of 1.4cfh ₂The product that obtains under nitrogen atmosphere room temperature storage 16 hours, then through diatomite filtration.The sulphur content of product is a 8.2%(weight), sodium content is a 18.2%(weight).

Example A-49

At 130 ℃, in 15.5 hours, feed the SO of 320 grams (10.0 equivalent) in the product that obtains by example A-44 toward 1750 grams (10 equivalent) with the flow velocity of 1.0cfh ₂The product diatomite filtration that obtains.The sulphur content of product is a 7.26%(weight), sodium content is a 12.6%(weight), boron content is 6.06%(weight).

Example A-50

At 140 ℃, in 15 hours, feed 640 gram (20 equivalent) SO in the product that obtains by example A-43 toward 3480 grams (20 equivalent) with the flow velocity of 1.35cfh ₂In reaction mixture, fed nitrogen 0.5 hour then.Obtain the desired product of 3570 grams with the diatomite filtration reaction mixture.Its sulphur content is a 8.52%(weight), sodium content is a 13.25%(weight).

Sulphur or sulphur source (B)

Component (B) can be elementary sulfur and/or at least a sulphur source.The sulphur source can be to provide any in the various materials of sulphur to reaction.The example in useful sulphur source comprises halogenation sulphur, the combination of sulphur or sulfur oxide and hydrogen sulfide and various sulfurized organism as described below.Elementary sulfur is a kind of being easy to get, useful active sulphur source.Useful halogenation sulphur comprises sulfur monochloride, sulfur dichloride etc.Sulphur and sulfur oxide (like SO ₂) and the combination of hydrogen sulfide also be useful sulphur source.

In one embodiment, the sulphur source is the compound of one or more sulphur couplings described in above-mentioned subhead " organic compound (A) (I) that the functional group of sulphur coupling replaces (f) ".A kind of useful sulphur source is 2,2 '-two sulphur, two isobutyric aldehydes.

The sulphur source can be at least a phosphoric sulfide also, and example comprises P ₂S ₅, P ₄S ₇, P ₄S ₃And P ₂S ₃

The sulfuration organism for preparing sulfuration high alkalinity product of the present invention as sulphur source (B) can be fragrance and alkyl sulfur compounds such as dibenzyl disulfide, bis-xylene base sulphur, two hexadecyl sulphur, two paraffinic base sulphur and polysulfides, cracked wax olefin sulfide etc.A kind of method of preparation fragrance and alkyl sulfur compounds comprises hydrochloric ether and a kind of inorganic sulphide condensation, and the free valency that the chlorine atom at this moment per two branches is substituted ， And and each molecule all connects the sulphur atom to one two valency.Generally, reaction is to carry out under the condition that elementary sulfur exists.

The example of two alkenyl sulphur that is used to prepare creative sulfuration high alkalinity product of the present invention is at United States Patent (USP) 2,446, is described in 072.These sulfide can react to each other under generally with the zinc of hydrochlorate form or condition that similarly metal exists by a kind of alkene that contains 3 to 12 carbon atoms and elementary sulfur and make.The example of such sulfide comprises 6,6 '-two sulphur two (5-methyl-4-nonene), crotyl-sulfide and disulphide, and 2-methyl-2-butene base-sulfide and disulphide.

The olefine sulfide that uses as the sulphur source comprise by with a kind of alkene (preferably containing 3-6 carbon atom) or by its institute's deutero-low-molecular-weight polyolefin and a kind of sulfocompound such as sulphur, sulfur monochloride and/or sulfur dichloride, hydrogen sulfide etc. react and the olefine sulfide that makes.The sulfurized organic compound can be a sulfuration oils, it can be by natural or synthetic oils, comprise mineral oil, lard, by Fatty Alcohol(C12-C14 and C12-C18) and lipid acid or aliphatic carboxylic acid deutero-carboxylicesters (for example oleic acid n-tetradecane base ester and Oleyl oleate), Sperm whale oil and synthetic Sperm whale oil surrogate, and synthetic unsaturated ester or glyceryl ester and make.Stable sulfide mineral lubricating oil can make like this, promptly a kind of suitable mineral lubricating oils and about sulphur of 1 to 5% about more than 175 ℃, preferably heat a few hours, to make a kind of reaction product that copper is not had basically corrosive nature at about 200 ℃ to about 260 ℃.The sulfurized mineral lubricating oils can be by paraffinic hydrocarbon in this way, the distillate or the Residual oil that obtain in the thick product of naphthenic hydrocarbon or mixed base.Similarly, sulfide fat oil such as sulfuration lard can be by making in the fully long time of about 150 ℃ temperature heating lard and about sulphur of 10% to 15% to obtain the such method of all thick product.

Can be by sulphur as the sulfide aliphatic acid ester in sulphur source, sulfur monochloride, and/or sulfur dichloride reacts with a kind of undersaturated fatty acid ester at elevated temperatures and makes.Typical ester comprises C ₈-C ₁₄The C of unsaturated fatty acids such as Zoomeric acid, oleic acid, ricinolic acid, petroselinic acid, vaccenic acid, linolic acid, linolenic acid, oil-stearic acid (Oleostearic), 18 carbon triolefin-11-ketone acid etc. ₁-C ₁₂Alkyl ester.Also is useful by the blended unsaturated fatty acid ester such as the sulfurized fatty ester that is prepared by animal tallow and vegetables oil such as Yatall MA, Toenol 1140, sweet oil, Viscotrol C, peanut oil, rape oil, fish oil, spermaceti wet goods.The specific embodiments of the sulfureted fatty acid ester of energy comprises Witconol 2301, ethyl oleate, oleic acid dodecyl ester, oleic acid hexadecane base ester, linolic acid hexadecane base ester, ricinolic acid 12 carbon alkyl esters, linolic acid grease, stearic acid grease and alkyl glycerol ester.

The sulfur-containing organic compound that an other class can be used as the sulphur source comprises the ester of sulfurized olefinic monobasic or di-carboxylic acid.For example, the Fatty Alcohol(C12-C14 and C12-C18) that contains 1 to 30 carbon atom can be used to the esterification monocarboxylic acid such as vinylformic acid, methacrylic acid, 2,4-pentadienoic acid etc., or fumaric acid, toxilic acid, muconic acid etc.The sulfuration of these esters is to use elementary sulfur, and sulfur monochloride and/or sulfur dichloride are implemented.

An other class sulfurized organic compound is the diester sulfide by following general formula representative:

S _y（（CH ₂） _xCOOR） ₂

Wherein X is about 2 numbers to about 5 scopes; Y is 1 a number to about 6 scopes, preferably 1 to about 3; R is one and contains about 4 alkyl to about 20 carbon atoms.The R group can be straight chain or fork chain, but wants enough big to keep the solubleness of composition of the present invention in oil.Typical diester comprises the sulfo-di-carboxylic acid such as propionic acid, butyric acid, valeric acid, the butyl of caproic acid, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, n-tridecane base, n-tetradecane base, the pentadecane base, hexadecane base, heptadecane base, octadecyl, 12 carbon alkyl and petrosilane base diester.In these diester sulfide, specific embodiment is 3,3 '-the two 12 carbon alkyl esters of thio-2 acid.

Olefine sulfide (B) as the sulphur source

In a specific embodiments, sulphur source (B) is at least a sulfurized alkene.This comprises that those can be according to United States Patent (USP) 2,708,199 method, and the Xi Ting And that contains 4 or more carbon atoms by chlorosulphonation further handles the organic polysulfide that makes with inorganic higher polysulfide.This patent content is herein incorporated by bibliography.

In a specific embodiments, olefine sulfide follows these steps to produce: (1) is sulfur monochloride and the excessive low carbon atom olefine reaction of stoichiometry, (2) the product that obtains in a kind of alcohol-water solvent, under the condition that free sulphur exists, handle with a kind of alkali metalsulphide by the mol ratio that is no less than 2: 1, (3) are product and the reaction of a kind of mineral alkali.This schedule of operation is a United States Patent (USP) 3,471,404 descriptions.Since the discussion of the relevant olefine sulfide for preparing the method for olefine sulfide and make in this schedule of operation, United States Patent (USP) 3,471, and 404 disclosed contents are by being incorporated herein by reference.Generally, olefin reactant contains about 2 to 5 carbon atoms, and specific embodiments comprises ethene, propylene, butylene, iso-butylene, amylene etc.In brief, in the first step, sulfur monochloride reacts in the ratio of one to two mole of alkene of every mole of sulfur monochloride.Reaction is to implement by mixed reactant under by about 20 ℃ to 80 ℃ temperature; In second step, be that preferably sodium sulphite and sulphur one react product and a kind of alkali metalsulphide of the first step reaction.To contain the about 2.2 moles metallic sulfide ， And of as many as and alkali metalsulphide be that every mole (1) step product has about 0.8 to about 1.2 mole metal sulfide to the mol ratio of the first step product to every grammeatom sulphur in the mixture.Generally, the reaction of second step is in a kind of alcohol or a kind of alcohol-water solvent, carries out under the condition that refluxes.The 3rd step of method be contain by about 1 to the phosphorus olefine sulfide of about 3% chlorine in the aqueous solution and the reaction between a kind of mineral alkali.The available bases metal hydroxides is such as sodium hydroxide.Reaction is proceeded to reduce to below 0.5% up to cl content, and this reaction was under refluxad carried out about 1 to 24 hour.

The olefine sulfide that is used for the present composition also can react under the condition that a kind of catalyzer exists by the mixture at following alkenes compound of superatmospheric pressure and sulphur and hydrogen sulfide, removes low-boiling point material then and prepares.The schedule of operation that is used for this preparation vulcanising composition of the present invention is a United States Patent (USP) 4,191,659 descriptions, owing to the description of the useful vulcanising composition of its preparation, the disclosure of this patent is herein incorporated by bibliography.The selective final step of in this patent, describing, be by, for example, handle with alkali metalsulphide, remove active sulphur.

Can be various as the olefin(e) compound in sulphur source in nature by this scheme Liuization And.They contain at least one olefinic double bond, and it can be appointed as nonaromatic pair of key; That is the two keys that, connect two fatty carbon atoms.On its wide significance, alkene can define with following formula:

R ¹R ²C＝CR ³R ⁴

Each R wherein ¹, R ², R ³And R ⁴Be hydrogen or an organic group.Generally, not that the R group of hydrogen can be such as-C(R in the following formula ⁵) ₃,-COOR ⁵,-CON(R ⁵) ₂,-COON(R ⁵) ₄,-COOM ,-CN ,-X ,-YR ⁵Or Ar, wherein:

Each R ⁵Be hydrogen independently, alkyl, thiazolinyl, aryl, the alkyl of replacement, the thiazolinyl of replacement or the aryl of replacement, condition is any two R ⁵Base can be the alkylidene group of alkylidene group or replacement, can form the ring of about 12 carbon atoms of as many as by it;

M is the metal ion (preferably I or II family, sodium for example, potassium, barium, calcium) of monovalent;

X is halogen (for example chlorine, a bromine or iodine);

Y is oxygen or divalent sulfur;

Ar is aryl or the aryl that contains the replacement of about 12 carbon atoms of as many as;

R ¹, R ², R ³And R ⁴In any two alkylidene groups that also can form an alkylidene group or replacement together; Be that the alkenes compound can be an alicyclic ring.

Substituent character generally is not critical in above-mentioned replacement partly, and the such substituting group of any class all is useful, promptly as long as it is maybe can make it be and lubricate environmentally compatible And and can not take place to disturb just under the reaction conditions of expectation.Like this, those are very unstable so that the compound of the replacement that rotten property ground decomposes under the reaction conditions that uses is just inapplicable.But some can be vulcanized as expecting such as ketone or aldehydes substituting group.Selecting suitable substituents is that skilled professional and technical personnel should be able to be competent at, and perhaps can determine by the test of routine.Typical this class substituting group comprises above-named any and hydroxyl, amidino groups, and amino, alkylsulfonyl, sulfinyl, sulphonate-base, nitro, phosphate-based, phosphorous acid ester group, basic metal sulfydryl etc.

The alkenes compound normally those wherein each is not that the R group of hydrogen is alkyl independently, the compound of the corresponding group that replaces of of thiazolinyl or aryl or (rare).Monoolefine and diolefin compound, particularly the former is through preferred compound, especially end group monoene hydro carbons; Be those R wherein ³And R ⁴Be hydrogen, R ¹And R ²Be alkyl or aryl, the compound of alkyl (being that alkene is fatty alkene) particularly.Have about 3 to 30, the vinyl compound of particularly 3 to 16 (the most frequently used is to be less than 9) carbon atoms is specially suitable.

Iso-butylene, propylene and their dimer, the mixture that the tripolymer and the tetramer and they are formed is particularly preferred olefin(e) compound.In these compounds, iso-butylene and diisobutylene can make extra high sulfur-containing compositions owing to their being easy to get property with by them, thereby are specially suitable.

The sulphur of merchandise resources and hydrogen sulfide generally are used to vulcanization reaction.The impurity that wherein has usually can allow existence and not have disadvantageous result.For example, the commodity diisobutylene believes and mainly comprises two kinds of isomeric forms that this mixture can be used among the present invention.

The sulphur of every mole of alkenes compound correspondence and the consumption of hydrogen sulfide do for oneself about 0.3-3.0 grammeatom and about 0.1-1.5 mole.Useful scope each about naturally 0.5-2.0 grammeatom and about 0.4-1.25 mole.Under the situation of periodical operation, each reactant promptly is introduced into the level that these ratio of components scopes can be provided.In the operation of semicontinuous and continuity, they are can any ratio mixed, but on the basis of material balance, they should exist with such amount, and the amount that makes each reactant be consumed is within these ratio ranges.Like this, for example, if pack sulphur at first separately in reaction vessel, then alkenes compound and hydrogen sulfide should add gradually with a kind of like this speed, make it possible to the ratio of components that reaches required.

The temperature range that vulcanization reaction carries out generally is about 50-350 ℃.Through preferred range is about 100-200 ℃, and specially suitable is about 125-180 ℃.Reaction is implemented under superatmospheric pressure; This can be autogenou pressure (i.e. spontaneous pressure in reaction process) usually, but also can be the pressure that adds.The accurate pressure that produces in reaction process depends on some factors, such as the design and the operational circumstances of system, and temperature of reaction, the vapour pressure of reactant and product ， And and it may change in reaction process.

The material that mixes in reaction mixture as the vulcanization reaction catalyzer usually is good.These materials can be acidity, alkalescence or neutral.Useful neutrality and acidic substance comprise acid-treated clay such as " Super Filtrol ", and to a toluenesulphonic acids, acid of dialkyl group phosphorus dithio and phosphoric sulfide are such as thiophosphoric anhydride.

Through preferred catalyzer is alkaline matter.This can be inorganic oxide compound and salt such as sodium hydroxide, calcium oxide and sodium sulphite.But the most desirable basic catalyst is that nitrogenous alkali comprises ammonia and amine.Amine comprises one-level, secondary and three grades of alkylamines, and alkyl wherein is an alkyl, aryl, aralkyl, alkaryl ， And and contain about 1-20 carbon atom.Suitable amine comprises aniline, benzylamine, dibenzylamine, 12 carbon alkylamines, morpholine, naphthylamines, tallow amine, N-ethyl dipropylamine, N-phenylbenzyl amine, N, N-diethyl butylamine, meta-aminotoluene and 23 dimethyl aniline.Also usefully heterocyclic amine such as Pyrrolidine, N-methyl Pyrrolidine, piperidines, pyridine and quinoline.

The consumption of catalytic specie is general about to be the 0.05-2.0% of alkenes compound weight.For the situation through preferred ammonia and amines catalyst, every mole of alkene is preferably used about 0.0005-0.5 mole, and desirable especially is the 0.001-0.1 mol catalyst.

Also can have water in reaction mixture, or it is as a kind of catalyzer, or as the thinner of one or more catalyzer of quoting as proof above.When having water, its amount generally is about 1-25% weight percentage of alkenes compound.But the existence of water is not absolutely necessary, and when using the conversion unit of some type, carries out under the substantially anhydrous condition and may be good being reflected at.

This method does not normally have beyond dewater to carry out under the situation of solvent and thinner.But sometimes in reaction with a kind of be inert substantially, generally be that liquid organic thinner may be desirable.The character of suitable diluent should be conspicuous to the skilled personnel of this specialty.

Finishing the required time of reaction will be according to reagent, their ratio, and whether temperature of reaction exists the factors vary such as purity of catalyzer and reagent, can follow the tracks of reaction process easily by the pressure in the monitoring reaction container.Reaction can be considered to finish when stress level is tending towards steady state value.

After preparing cured blend with above-mentioned experimental arrangement, all low-boiling point materials all are removed basically.The character of these low-boiling point materials will be according to the amount of used reactant and type and reaction conditions and is changed.The apparatus that it also can be placed into according to sulfur product to a certain extent, and such as the consideration of smell and flammable aspect.Reactant and by product round-robin again need wait this class factor and change.The most frequently, product should have about flash-point more than 30 ℃, and is preferably about more than 70 ℃, and desirable is more than 100 ℃, and this available this standard program of ASTM Procedure D93 is measured.Also can be with reference to ASTM Procedure D56 and D1310.

Except such as this class raw material of olefin(e) compound, low-boiling point material will usually comprise thio-alcohol and monosulphide class, particularly contain when being less than 9 carbon atoms when the alkene of initial usefulness.Product preferably comprises this class raw material, mercaptan and monosulphide of no more than about 5% weight percentage in these cases.If these materials are gas under the pressure and temperature condition of environment, then they can be by ventilation and removed ， And partially and they can be circulated again if desired in the reaction vessel simply.For the situation of the less raw material of volatility, have necessity and seek help from such as air distillation or such technology such as vacuum distilling or stripping.Another kind of useful method is that a kind of rare gas element such as nitrogen is passed through reaction mixture under suitable temperature and pressure condition.Large-scale gas-chromatography and molecular distillation also may be useful.

Any solid that is present in the reaction mixture can be removed easily, in most of the cases, only needs product liquid is inclined to get final product, if further remove solid, the technology of available routine is such as filtration and centrifugal.

The precise chemical structure character of the vulcanising composition that makes in this way knows also imprecisely, most convenient be to describe them by means of their method of preparation.But it seems that when being less than 9 by containing, when the alkene that particularly is less than 7 carbon atoms was prepared, they mainly contained disulphide, trisulphide and tetrasulfide.The sulphur content of these vulcanising compositions generally is approximately the 2-60% weight percentage, preferably about 25-60%, and the most desirable is about 40-50%.

Available following example B-1 to B-4 illustrates the preparation of olefine sulfide.

Example B-1

526 gram sulphur (16.4 moles) are packed in the high-pressure reactor that agitator and inner spiral coil cooling tube are housed of strap clamp cover.In coil pipe, freeze circulating in of salt solution and make reactor cooling before introducing gas reactant by vapour.After the sealed reactor, it is evacuated to 2 Tuo And cooling, charging 920 gram (16.4 moles) iso-butylenes and 279 restrain (8.2 moles) hydrogen sulfide in the reactor.Make temperature in 1.5 hours, rise to about 182 ℃ with the steam-heated cal(l)andria reactor in the chuck outside, in this heat-processed, in the time of about 168 ℃, reach maximum pressure 1350Psig(pound/square inch gauge).Before the peak value that arrives temperature of reaction, pressure promptly begins to reduce ， And and continues to descend along with gas reactant is consumed pressure-stabilisation ground.After under about 182 ℃ temperature of reaction about 10 hours, force value is 310-340Psig, and the speed of pressure change is 5-10Psig per hour.Unreacted hydrogen sulfide and iso-butylene are vented in the recovery system.After pressure in reactor had been reduced to barometric point, cured blend was recovered as liquid.

About 100 ℃ with the nitrogen purging reaction mixture to remove the low-boiling point material that comprises unreacted iso-butylene, mercaptan and monosulphide etc.Resistates behind nitrogen purging and 5% ^*Super Filtrol Yi plays Jiao Ban And and filters with super-cell.Filtrate is required vulcanising composition, and it contains the sulphur of 42.5% weight percentage.

Example B-2

151 gram sulphur are packed into and are similar in the sort of reactor of describing among the example B-1.Sulphur is heated to 160 ℃ And reactor is sealed, and vacuumizes.In about 4.5 hours, slowly in reactor, add 72 gram hydrogen sulfide.After this, after approximately adding 3.8 parts of hydrogen sulfide, promptly add 1.6 gram catalyzer n-Butyl Amine 99s.Then, 157 gram iso-butylenes are added by this way at leisure contains sulphur, in the reactor of catalyzer and about 10 parts of hydrogen sulfide, the speed that makes iso-butylene and hydrogen sulfide add can be kept hydrogen sulfide 10% molar excess, is added in the reactor up to all hydrogen sulfide.Continue to add remaining iso-butylene till all 157 grams all are added into.Temperature is maintained at that And needs to cool off reactant occasionally Nei 160-170 ℃ the Fan Wei in whole above-mentioned fill process.Be reflected at 171 ℃ and kept 5 hours, then unreacted hydrogen sulfide and iso-butylene are vented to that the pressure in reaction vessel is reduced to barometric point in the recovery system.By separate in the reacting coarse product low-boiling point material can by with nitrogen purging then the method for vacuum-evaporation finish.Then resistates is filtered, filtrate is required vulcanising composition, and it contains the sulphur of 47% weight percentage.

Example B-3

2025 gram sulfur monochlorides (15.0 moles) are heated to 45 ℃.In 5 hours by restrain the isobutene gas of (26.2 moles) in the charging 1468 in the reactor of subsurface gas distributor.Temperature maintenance is between 45-50 ℃.When finishing the distribution charging, reaction mixture weightening finish 1352 grams.

In the another one reaction vessel, add 2150 gram (16.5 moles) 60% Sodium Sulfide Flakes, 240 gram (7.5 moles) sulphur and 420 milliliters of solution that Virahol forms in 4000 ml waters.Content is heated to 40 ℃, and the sulfur monochloride that adding makes previously in 45 minutes and the affixture of iso-butylene allowable temperature simultaneously are raised to 75 ℃.Reaction mixture refluxed 6 hours, allow mixture to form separately two-layer then.Discard lower aqueous layer.Top organic layer refluxes mixture 6 hours with 2 liters, 10% sodium hydroxide mixing ， And.Shift out organic layer again, with a liter water washing.Through the product of washing under 90 ℃ and 30mmHg column pressure dry 30 minutes.Resistates promptly provides 2070 through the super-cell filtration and restrains the limpid bisque liquid that is.

Example B-4

The 102.8 gram sulfur monochlorides of packing in the reactor under nitrogen atmosphere, later entire reaction all maintains under the nitrogen atmosphere, the gas iso-butylene that restrains by the charging about 718.5 in the reactor of subsurface pipeline.Iso-butylene should add as quickly as possible, keeps the highest still temperature at about 49 ℃ with a cooling bath bundle simultaneously.After all iso-butylenes were added into, the reduction of still temperature was finishing of Indicator Reaction.

In a container that separates, prepare a mixture by 340.3 gram 18% sodium sulfide solutions and 363.8 grams, 50% aqueous sodium hydroxide solution.128.77 gram 55.7% Virahols that reclaim in the primary first-order equation before adding and the mixture of water.This is equivalent to 71 gram exsiccant Virahols.Mixture is stirred, and Xun Huan And is heated to about 74 ℃ temperature at 2 hours internal reflux.Keeping the still temperature in about 75-80 ℃, the 168.13 gram iso-butylenes that prepare above in 5 hours, adding, the reaction product of sulfur monochloride.Reaction mixture stirred about 5 hours at about 80 ℃ of Wei Chi And, then mixture was cooled to about 38 ℃ And and allowed its sedimentation.Organic phase (138.7 gram) is evaporated any residual water and volatile matter by the water And that is separated.Under agitation in resistates, add flocculating aids, then approximately 50-65 ℃ mixture filtered, filtrate is desired product, it contains the sulphur of about 43% weight percentage.

Sulfurized Diels-Alder adducts as sulphur source (B)

In a specific embodiments, sulphur source (B) is ring-type or the bicyclic alkene derived from a kind of particular type, and they are the Diels-Alder adductss that formed by at least a dienophile and at least a fatty conjugated dienes.Sulfurized Diels-Alder adducts can be by various sulfuration reagent and below the Diels-Alder adducts of more detailed description is reacted and make.Preferably, sulfuration reagent is sulphur.

The Diels-Alder adducts is that a class can or be called Diels-Alder by diene synthesis and reacts the compound that prepare well-known, specialty are generally acknowledged.The summary of relevant this compounds in prior art can be referring to one piece of thematic treatise of following Russia: Dienovyi Sintes, Izdatelstwo Akademii Nauk SSSR, 1963, the author is turned into English by L.Mandel for A.SOnischenkO.(: A.S.Onischenko, Diene Synthesis, N.Y.Daniel Davey and Co., Inc., 1964).The document that quote as proof this piece disquisition and it all is incorporated in the patent specification by bibliography.

Adducts and the method for preparing adducts can further illustrate with following example B-5 to B-8.

Example B-5

Containing 400 gram toluene, the mixture of 66.7 gram aluminum chloride is packed into agitator is housed, and nitrogen inlet tube is in the 2 liter bottles of solidified carbon dioxide refrigerative reflux condensing tube.When holding temperature is in 37-58 ℃ of scope, in 0.25 hour, second mixture that contains 640 gram (5 moles) butyl acrylates and 240.8 gram toluene is added to above-mentioned Alcl ₃In the slurries.Then, the temperature maintenance that makes reactive material by exterior cooling added 313 gram (5.8 moles) divinyl in slurries in 2.75 hours in 50-61 ℃.Reactant about 0.33 hour with nitrogen purging, the separating funnel Zhong And that transfers to one 4 liter then restrains the solution washing that forms in the water with 150 gram concentrated hydrochloric acids 1100.Subsequently, product is used other washing twice again, at every turn with 1000 gram water.Then the reaction product of washing is distilled to remove unreacted butyl acrylate and toluene.This for the first time the distillatory resistates taken away and under the 9-10 mmhg pressure, further distilled, collect the desired product of 785 grams 105-115 ℃ temperature.

Example B-6

By in a swing autoclave, mixing 136 gram isoprene, 106 gram vinyl cyanide and 0.5 gram quinhydrones (stopper),, can make the adducts of isoprene and vinyl cyanide then 130-140 ℃ temperature range internal heating 16 hours.Autoclave Fang Kong And content therefrom incline to obtain 240 the gram weak yellow liquids.This liquid is evaporated under 90 ℃ temperature and 10mmHg column pressure, and the resistates that its produces is desired product liquid.

Example B-7

With the schedule of operation of example B-6,136 gram isoprene, 172 gram methyl acrylates and 0.9 gram quinhydrones are converted into the adducts of isoprene methyl acrylate.

Example B-8

Heavily cover the schedule of operation of example B-6, just have only 270 gram (5 moles) divinyl to be comprised in the reaction mixture specifically.

Sulfocompound can be easy to heat a kind of mixture that vulcanizes the Diels-Alder adducts formation of reagent such as sulphur and at least a the sort of type discussed above and make by extremely being lower than in the temperature range of Diels-Alder adducts decomposition temperature just at about 110 ℃.Usually used temperature about 110 ℃ to about 200 ℃ scope.This reaction produces the mixture that some products are formed, and wherein some are identified.In the compound of known structure, sulphur and replacement, the reaction of undersaturated ring-shaped fat reactant is on two keys of the nuclear of unsaturated reactant.

Being used for preparing sulfur-containing compositions sulphur is by about 0.5: 1 to about 10: 1 to the mol ratio of Diels-Alder adducts, though general used mol ratio was less than about 4: 1.In a specific embodiments of the present invention, mol ratio is less than about 1.7: 1 ， And and more preferably less than about 1: 1.

Vulcanization reaction can be at a kind of suitable inert organic solvents such as mineral oil, contains under the condition of existence such as alkane of 7 to 18 carbon atoms to carry out, and be general necessary though there is not solvent.After reaction is finished, the purification process that reactant can filter and/or other is common.There is no need to separate various sulphur products, because the form of reaction mixture that they can contain the compound of known and unknown structure is used.

Remove H ₂S is good sometimes.This can pass through to use steam, alcohol, and air or nitrogen purging are realized.Also can under the condition that purges or do not have to purge, realize by under reduced pressure, heating.

The material that mixes in reaction mixture as sulphurized catalyst is good sometimes.These materials can be tart, alkalescence or neutral.Useful neutrality and acidic substance comprise acid clay such as " Super Filtrol ", tosic acid, the acid of dialkyl group phosphorus dithio, phosphoric sulfide such as thiophosphoric anhydride and phosphorous acid ester such as triaryl phosphites (for example triphenyl phosphite).

Alkaline matter can be inorganic oxide and salt such as sodium hydroxide, calcium oxide and sodium sulphite, still, the most desirable basic catalyst is that nitrogenous alkali comprises ammonia and amine.Amine comprises one-level, secondary and three grades of alkylamines, and alkyl wherein is the alkyl that contains about 1-20 carbon atom, aryl, aralkyl or alkaryl etc.Suitable amine comprises aniline, benzylamine, dibenzylamine, 12 carbon alkylamines, naphthylamines, tallow amine, N-ethyl dipropylamine, N-phenylbenzylamine, N, N-diethyl butylamine, meta-aminotoluene and 23 dimethyl aniline.Also available heterocyclic amine such as Pyrrolidine, N-methyl Pyrrolidine, piperidines, pyridine, morpholine and quinoline.

When using catalyzer, its consumption is general about to be the 0.05-2.0% of adducts weight.

Following example B-9 to B-14 has illustrated the preparation by Diels-Alder adducts deutero-sulfocompound.

Example B-9

In 45 minutes,, add 53 gram (1.65 moles) sulphur powder toward being heated in 255 gram (1.65 moles) isoprene-methacrylic ester adductss of example B-7 of 110-120 ℃.In 130-160 ℃ temperature range, continue heating 4.5 hours.Behind the cool to room temperature, reaction mixture filters through the medium size sintered glass funnel.Filtrate is contained the desired sulphur products of 301 grams.

Example B-10

The reaction mixture of the Diels-Alder adducts that comprises 1175 gram (6 moles) butyl acrylates and isoprene and 192 gram (6 moles) sulphur powder was heated 0.5 hour at 108-110 ℃ earlier, then 155-165 ℃ of heating 6 hours, simultaneously in reaction mixture, feed nitrogen with 0.25 to 0.5cfh flow velocity.Unfinished in heat-up time allows reaction mixture Leng Que And to filter in room temperature.Then, allow product place 24 hours, filter again, filtrate is required product.

Example B-11

Sulphur (4.5 moles) and isoprene-methyl methacrylate adducts (4.5 moles) were heated one hour at 110 ℃ at room temperature Hun He And, and the nitrogen with flow velocity 0.25-0.5cfh passes through reactive material simultaneously.Reaction mixture is warming up to 150-155 ℃ of heating 6 hours subsequently, keeps the purging of nitrogen simultaneously.After the heating, allow reactive material to place a few hours, cool to room temperature filters then simultaneously, and filtrate comprises the required sulphur products of 842 grams.

Example B-12

In a reaction vessel, prepare one by the butyl acrylate-divinyl adducts that makes among 1703 gram (9.4 moles) example B-8, the mixture that 280 gram (8.8 moles) sulphur and 17 gram triphenyl phosphites are formed.And was heated to about 185 ℃ to it gradually in 2 hours under the condition of stirring and nitrogen purging.Be heat release near being reflected at 160-170 ℃, mixture kept 3 hours at about 185 ℃.Mixture ℃ filters with flocculating aids then at 2 hours internal cooling to 90.Filtrate is required product, and it contains the sulphur of 14% weight percentage.

Example B-13

Heavily covering the experimental arrangement of example B-12, is without triphenyl phosphite in reaction mixture.

Example B-14

Heavily cover the experimental arrangement of example B-12, just replace triphenyl phosphite as sulphurized catalyst with 2.0 gram triamylamines.

Sulfuration terpenes as sulphur source (B)

The sulphur source can be at least a sulfurized terpene compound or a kind ofly comprise at least a terpenes and the prepared composition of at least a other alkenes compound by sulfuration.

Term " terpene compound " here is to want to be used for comprising that having empirical formula is C ₁₀H ₁₆The terpene hydrocarbons of various isomeries.Such as being included in turps, those in pine tar and the Dipentine and various synthetic and naturally occurring their containing oxygen derivative.Generally be to use the mixture of these different compounds, especially when using natural product such as pine tar and turps.For example, the pine tar by useless pine destructive distillation is obtained comprises by terpenes derivative such as alpha-terpineol, β-Terpineol 350, α-fenchol, camphor, borneol/iso-borneol, fenchone, estragole, dihydro-, formed mixtures such as methyl allylphenol and other monoterpene hydro carbons.The concrete ratio of various components and content will depend on the specific source and the degree of purifying in given pine tar.Can buy a class pine tar deutero-product by Hercules Incorporation company.Have been found that the pine tar product of being bought by Hercules Incorporation company that is commonly referred to as terpenol is useful especially when the preparation that is used for sulfur product of the present invention.The example of this class product comprises the alpha-terpineol that contains the 95-97% alpha-terpineol, typically comprises three grades of terpenol mixtures of a kind of high purity of 96.3% tertiary alcohol; Tcrpineol 318 Prime are mixtures of a kind of isomery Terpineol 350 that obtains by the dehydration of terpene hydrate, and it comprises the alpha-terpineol of about 60-65 weight percentage and β-Terpineol 350 and other three grades of terpenols of 18-20% of 15-20%.The useful pine tar product of other mixture and other grade also can have been bought by Hercules company, and its trade name is Yarmor 302, Herco pine tar, Yarmor 302W, YarmorF and Yarmor 60.

The terpene compound that can be used as the sulphur source can be the sulfurized terpene compound, the mixture of sulfurized terpene compound or the mixture of being made up of at least a terpene compound and at least a sulfurized terpene compound.The sulfurized terpene compound can be by use sulphur, halogenation sulphur, or the mixture of sulphur or carbonic acid gas and hydrogen sulfide composition vulcanizes terpene compound and make, as following will be more fully as described in.The vulcanization reaction of various terpene compounds also is described in prior art, and for example, the sulfuration of pine tar is at United States Patent (USP) 2,012, is described in 446.

Other alkenes compound that can be used in combination with terpene compound can be some alkenes compounds, any such as in those alkene of describing in previous subhead " as the olefine sulfide in sulphur source (B) ".

Other alkene that is used in combination with terpene compound also can be a kind of undersaturated lipid acid, undersaturated lipid acid, their mixture, or the mixture of they and above-mentioned alkene.Terminology used here " lipid acid " is meant the acids that those can make by fat or the oil of naturally occurring plant of hydrolysis or animal.These lipid acid generally contain by about 16 to about 20 carbon atom ， And and are saturated and mixture unsaturated fatty acids.Generally the unsaturated acid that comprises in the fat of naturally occurring plant or animal and oil contains one or more pairs of keys, and this class acid comprises Zoomeric acid, oleic acid, linolic acid, linolenic acid and erucic acid.

Unsaturated fatty acids can contain the mixture of number acid, and is oily as lard by naturally occurring animal and plant such as those, Yatall MA, peanut oil, soybean oil, Oleum Gossypii semen, the unsaturated fatty acids that obtains in sunflower seed oil or the wheatgerm oil.Yatall MA is a sylvic acid, mainly is abietic acid, and unsaturated acid, mainly is oleic acid and linoleic mixture, and Yatall MA is the by product that sulphate process is made wood pulp.

Mixing some materials as vulcanization reaction promotor in reaction mixture usually is good.These can be that acidity, alkalescence or neutral promotor were discussed in front.

The consumption of promotor material generally is about the 0.0005-2.0% of terpenes and olefin(e) compound gross weight.For with the situation through preferred ammonia and amines catalyst, preferably every mole of total olefin weight is with about 0.0005-0.5 mole promotor, and about 0.001-0.1 mole is desirable especially.

Water perhaps as the thinner of the promotor of quoting as proof again above one or more, also is present in the reaction mixture as a kind of promotor.When existing, the amount of water is generally the 1-25% weight percentage of olefin(e) compound.But be not absolutely necessary ， And and when using the conversion unit of some type of the Cun Zai And of water reacts under substantially anhydrous condition and may be good.

When mixing promotor in the reaction mixture as mentioned above, generally can be observed reaction, can to carry out the color of ， And and product under lower temperature general also lighter.

Being used for vulcanizing terpenic sulfuration reagent can be, for example, sulphur, halogenation sulphur is such as Sulphur Monochloride and sulphur dichloride, a kind of mixture of being made up of hydrogen sulfide and sulphur or sulfurous gas etc.The mixture of sulphur or sulphur and hydrogen sulfide usually is preferred.But, should understand, other sulfuration reagent also can replace them in due course.The merchandise resources of all sulfuration reagent is normally used for purpose of the present invention, and may not produce disadvantageous result with the Za Zhi And that these commodity exist together usually.

When carrying out vulcanization reaction with sulphur separately, only need in about 50 to 250 ℃ temperature, normally about 150 ℃ are heated reagent and sulphur together to about 210 ℃ temperature reaction is carried out.Terpenes and other alkene are between about 5: 1 to about 15: 1 to the weight ratio of sulphur together; generally be between about 5: 1 and about 10: 1; vulcanization reaction is under effective agitation condition, generally carries out under a kind of rare gas element (for example nitrogen) protection.If it is obviously volatile that any component or reagent are arranged under temperature of reaction, then reaction vessel answers Bei Mi Feng And to maintain under the pressurized conditions.In the mixture of other component, divide several parts adding sulphur usually to be good.

When using the mixture of sulphur and hydrogen sulfide, the sulphur that every mole of terpenes and other alkene are used and the amount of hydrogen sulfide do for oneself usually about 0.3 to about 3 grammeatom and about 0.1 to about 1.5 moles.Each about naturally 0.5 to 2.0 grammeatom of useful scope and about 0.4 to about 1.25 moles, the most desirable scope each about naturally 0.8 to about 1.8 grammeatom and about 0.4 to 0.8 mole.In periodical operation, they can any mixed, but on the basis of material balance, their exist amount they are consumed by the scope of these ratio of components.Like this, for example, if sulphur only is housed in the reaction vessel at first, then olefin(e) compound and hydrogen sulfide can such speed add gradually, make required ratio of components to reach.

When using the mixture of sulphur and hydrogen sulfide in vulcanization reaction, the temperature range of vulcanization reaction generally is by about 50 ℃ to about 350 ℃.Preferred range is about 100 ℃ to about 200 ℃, and specially suitable is about 120 ℃ to about 180 ℃.Reaction is usually implemented under superatmospheric pressure, and this can be autogenou pressure (i.e. spontaneous pressure in reaction process) usually, but also can be the pressure that adds.The accurate pressure that produces in reaction process depends on some factors, such as the design and the operational circumstances of system, temperature of reaction, the vapour pressure of reactant and product etc.And and it may change in reaction process.

Though preferred in general way is all to comprise component and mentioned reagent in the reaction mixture, reaction also can be carried out under the condition that a kind of inert solvent (for example a kind of alcohol, ether, ester, aliphatic hydrocarbon, halogenated aromatic etc.) exists.This solvent is a liquid the used temperature range planted agent of reaction.When temperature of reaction than higher, for example, in the time of about 200 ℃, may have some sulphur and from product, emit.When using lower temperature of reaction such as about 150-170 ℃, can avoid.

Finishing the required time of vulcanization reaction will rely on reagent, their ratio, and whether temperature of reaction exists the factor such as purity of promotor and reagent and changes.When the mixture of sulphur and sulfurous gas is used as sulfuration reagent ， And and reaction is that when carrying out, reaction process can be followed the tracks of easily by the pressure in the monitoring reaction container in the container of sealing under elevated pressure.Reaction can be considered to finish when stress level is tending towards steady state value.After preparing cured blend with above-mentioned experimental arrangement, generally preferably remove all basically low-boiling point materials, typical way is reaction vessel emptying, or distillation under atmospheric pressure, vacuum distilling or evaporation, or pass through reaction mixture such as nitrogen at following a kind of rare gas element of suitable temperature and pressure.Any solid that is present in the reaction mixture in most of the cases can be removed by the method that product liquid is inclined easily.If further remove solid, can use and filter or the common technology of centrifugal this class.

Following example B-15 to B-18 has explained the preparation process of mixture as the sulfuration terpene compound in sulphur source (B) and sulfuration terpenes and alkenes.

Example B-15

The pine tar that 372 grams (2 equivalent) of packing in the reaction vessel are bought.Under agitation pine tar is heated to 35 ℃.At Dan air-blowing Sao And temperature of reaction is maintained and slowly add 128 gram sulphur under about 35 ℃ condition.Add after the sulphur, by reaction mixture, the while is in about 145 ℃ of reflux with nitrogen bubble.After about 8 hours of one coreaction, by flocculating aids mixture is filtered, filtrate is desired sulfur product, and it contains the sulphur of 23.35% weight percentage.

Example B-16

Heavily cover the schedule of operation of example B-15, just contain 186 gram pine tars (1 equivalent) and 32 and restrain sulphur (1.0 equivalent) in reaction mixture, the sulphur content of the product that obtains with this method is 15.6% weight percentage.

Example B-17

In reaction vessel, add 372 gram (2 equivalent) pine tars and 96 parts of (3 gram) sulphur.After all sulphur adds, under nitrogen purging mixture heating up to 150 ℃ ， And mixture about 10 hours in this temperature maintenance.By flocculating aids reaction mixture is filtered, filtrate is desired product, and it has the sulphur content of 17.25% weight percentage.

Example B-18

Prepare a mixture of forming by 186 gram (1 equivalent) pine tars and 168 gram (1 equivalent) polypropylene, under agitation add the sulphur of 96 grams (3 equivalent).Under nitrogen purging reaction mixture being heated to about 170 ℃ And kept under this temperature 10 hours.Then reaction mixture Leng Que And is filtered by flocculating aids.Filtrate is desired product, and its sulphur content is 16.79% weight percentage.

Be used as the dithiocarbamate of the sulphur coupling in sulphur source (B)

In a specific embodiments, sulphur source (B) is the dithiocarbamate of a sulphur coupling that can be expressed from the next

R wherein ¹, R ²And R ³Be hydrogen or an alkyl independently; R ⁴Be H, OH or an alkyl; R ⁵And R ⁶Be H independently, alkyl or hydroxy alkylene; Perhaps R ³And R ⁴Together and/or R ⁵And R ⁶Together and/or R ¹And R ³Together and/or R ²And R ⁴Can form a cyclic group ， And and X together and be one by 1 to about 8 number.

Alkyl R ¹To R ⁴It can be the alkyl of straight chain or fork chain.Each R ¹To R ⁶Can contain 1 independently to about 100 carbon atoms, preferably 1 to about 30 carbon atoms.

Radicals R ¹To R ⁴Can be fat or aromatic group, such as alkyl, cycloalkyl, alkaryl, aralkyl or aryl.R ³And R ⁴Together and/or R ⁵And R ⁶Can be one together and contain about 4 alkylidene groups to about 7 carbon atoms.In these specific embodiments, R ³And R ⁴Continuing R with key in the formula V ³And R ⁴Carbon atom will form a cycloalkyl ， And and R together ⁵And R ⁶With the R that ins succession of key in the formula V ⁵And R ⁶Nitrogen-atoms form a heterocyclic group together.

Alkyl R ¹To R ⁶Specific embodiments comprise methyl, ethyl, sec.-propyl, isobutyl-, second butyl, cyclohexyl, cyclopentyl, octyl group, 12 carbon alkyl, octadecyl, twenty carbon alkyl, n-docosane base, three decane bases, phenyl, naphthyl, styroyl, octyl phenyl, tolyl, xylyl, two octadecyl phenyl, triethyl phenyl, chloro-phenyl-, methylamino-base phenyl, dibromo phenyl, nitrophenyl, 3-chlorine hexyl etc.

In a concrete scheme of the present invention, the dithiocarbamate of sulphur coupling can following structural formula be a feature:

S _x

CH（R ³）-CH（R ⁴）S（S）CNR ⁵R ⁶） ₂（Ⅴ-A）

(X is the number of 1-2 in the formula, R ³And R ⁴Be a H or an alkyl, R ⁵And/or R ⁶Respectively be respectively alkyl).Alkyl can be any alkyl of above-mentioned formula V.In general, R ⁵And R ⁶To contain about 50 carbon atoms of 1-, R ³And R ⁴For containing the alkyl of about 100 carbon atoms of 1-.

In a specific embodiments, dithiocarbamate is feature with the following formula:

(R in the formula ¹, R ², R ³, R ⁵, R ⁶With X such as following formula V definable).

In a specific embodiments, the preparation method of the dithiocarbamate of sulphur coupling comprises the following steps:

(A) with halogenation sulphur and (ⅰ) at least a alkene that waits stoichiometric quantity or (ⅱ) a kind of aldehydes or ketones under a certain temperature, react the sufficiently long time with generation dihalo alkyl sulphur intermediate or dialdehyde or diketone sulphur intermediate;

(B) with the reactant salt of the dithiocarbamic acid of intermediate and q.s, with dithiocarbamate-based replacement two halogen atoms, or with two carbonyl reactions of dialdehyde or diketone.

When raw material was (ⅰ) at least a alkene, the product that obtains was a feature with formula V or formula V-A, and perhaps product is to comprise that mainly with formula V and formula V-A be the mixture of feature.When raw material was (ⅱ) a kind of aldehydes or ketones, product was a feature with formula V-B mainly.

The halogenation sulphur that is used for step (A) can be that single sulfur subchloride (is S ₂Cl ₂), sulfur dichloride, single sulfur bromide, dibrominated sulphur or above-mentioned any halogenation sulphur are with the different amounts and the mixture of elementary sulfur.

Various alkene and alkene mixture all can be used as the raw material of step (A).The alkene mixture that is obtained by the oligomeric polymerization of ethene and/or propylene is than cheap.Alkene contains at least one olefinic double bond that is defined as the two keys of non-aromatics, promptly connects two keys of two aliphatic carbon atoms.Alkene can define by following formula:

R ¹R ³C＝CR ²R ⁴

(R in the formula ¹, R ², R ³And R ⁴Respectively be a hydrogen or an alkyl, as the following formula V, V-A or V-B define.Though can use diolefine, preferably use monoolefine, and be not hold monoolefine, be i.e. R in the alkene ¹And R ³Be hydrogen, R ²And/or R ⁴It is alkyl or aryl.Internal olefin compound, for example R ¹And R ²The compound that is alkyl or aryl also is suitable for.Contain about 100 carbon atoms of 3-, more generally be that the olefin(e) compound that contains about 30 carbon atoms of 3-is special ideal.

Iso-butylene, propylene and their dimer, tripolymer, the tetramers etc. and their mixture also are the olefin(e) compounds that is fit to.In these compounds, iso-butylene, diisobutylene, triisobutene and four iso-butylenes are because its validity and desirable especially.

The product that obtains with halogenation sulphur and one or more above-mentioned olefine reaction is that the element by halogenation sulphur adds to the dihalo alkyl sulphur intermediate that produces on the alkene unsaturated carbon atom.Though its speed of reaction can be increased by the temperature that improves mixture, reaction is because of carrying out alkene and mixing of halogenation sulphur.Therefore mixture generally is to be in approximately between-20 ℃ to about 120 ℃, finishes until reaction.Temperature of reaction is to be decided by the thermostability of the reactivity of raw material olefin and reaction product.

In addition, can be with alkene heat to temperature required, to wherein dripping halogenation sulphur, dripping generally is to carry out in inert atmosphere, its speed is enough to the temperature that keeps required.After adding halogenation sulphur, can with reaction mixture reheat for some time to finish reaction.

With the halogenation sulfur content of olefine reaction generally be the stoichiometric calculation equivalent.For example, when doing halogenation sulphur source, be that 1 mole single halogenation sulphur and 2 moles alkene or alkene mixture are reacted with single halogenation sulphur.

Can use catalyzer or reaction promotor, though they are generally considered to be unnecessary.The example of this catalyzer or promotor comprises low-grade aliphatic amine or aromatic amine, particularly tertiary amine.

The aldehydes or ketones that can be used as raw material and halogenation reaction of Salmon-Saxl can following formula be a feature:

R ¹R ³CHC（O）R ²

(R in the formula ¹, R ²And R ³Be a H or an alkyl independently, as the following formula V, shown in V-A or the V-B).As raw material is aldehyde, and intermediate will contain 2 aldehyde carbonyls; As raw material is ketone, and the sulphur intermediate will contain 2 ketone groups.

Aldehydes or ketones can with the halogenation reaction of Salmon-Saxl, as single sulfur subchloride, sulfur dichloride, single sulfur bromide, the mixture of dibrominated sulphur and halogenation sulphur and elementary sulfur.

The reaction of aldehydes or ketones and halogenation sulphur can be only get final product two reactants can needing to mix under the temperature, and temperature can be in-30 ℃ of pacts extremely about 250 ℃ or higher scopes.Preferred temperature generally about 10 ℃ to about 80 ℃ scope.Reaction can be carried out in thinner or solvent, as benzene, and petroleum naphtha, hexane, tetracol phenixin, chloroform, mineral wet goods.Diluent/solvent can make things convenient for the thorough mixing of temperature controlling and reactant.

Aldehydes or ketones can change in relative broad range the relative quantity of halogenation sulphur.In most examples, reaction comprises 2 moles aldehydes or ketones and 1 mole halogenation sulphur, and in other examples, one of reactant is available excessive.Contain sulphur compound as need more than 2 sulphur atoms (for example X is the integer of 3-8), can be with the mixture reaction of aldehydes or ketones and halogenation sulphur and sulphur.Normally with halogenation sulphur with aldehydes or ketones reaction before with reaction of Salmon-Saxl.

Can comprise for example acetaldehyde, propionic aldehyde, butyraldehyde, isobutyric aldehyde, 2-ethyl-1-hexanal, hexanaphthene formaldehyde (C with the specific embodiments of the aldehyde of halogenation reaction of Salmon-Saxl ₆H ₁₁CHO).The specific embodiments of ketone comprises Ketene dimethyl, methylethylketone, diethyl ketone, first isopropyl acetone, first isobutyl ketone etc.

The preparation of the dithiocar-bamate of sulphur coupling is with above-mentioned sulphur intermediate and the reaction of-dithiocar-bamate, the latter's amount need be enough to dithiocarbamate-based replacement halogen group or with two carbonyl reactions of dialdehyde or diketone intermediate.Dithiocar-bamate is representative with the following formula:

R ⁵R ⁶NC（S）SX

(R in the formula ⁵And R ⁶Respectively be hydrogen, alkyl or hydroxyl alkyl; X is a basic metal, tertiary amine or other alkaline matter).The available amine R of the preparation of dithiocar-bamate ⁵R ⁶NH and dithiocarbonic anhydride react in the presence of alkali.Alkali is normally used alkalimetal oxide, and mol ratio is 1: 1: 1.Alkali is preferably as sodium hydroxide, potassium hydroxide, the alkali metal hydroxide of sodium hydroxide more usually, but also can be tertiary amine or excess amine is used for reaction.

Alkyl or hydroxyl alkyl R ⁵And R ⁶Can contain 1 to about 50 carbon atoms, preferably lower alkyl.In one embodiment, R ⁵And R ⁶Be to contain about 4 alkenyls to about 7 carbon atoms, and in this embodiment, R ⁵And R ⁶Nitrogen-atoms on being connected in them will form a heterocyclic radical.Heterocyclic radical (and alkenyl) can contain other atom, as oxygen or sulphur.

Be used to form dithiocar-bamate and amine (R ⁵R ⁶NH) specific embodiments comprises for example methylamine, propylamine, dimethylamine, diethylamine, dipropyl amine, dibutylamine, thyl methyl amine, first hexahydroaniline, piperidines, morpholine, dihexylamine, Di-Octyl amine, two cocoa amines, dimethyl hydroxyethyl amine, diethanolamine, piperazine etc.

The dithiocarbamic acid metal-salt is the prior art known compound, can easily prepare with prior art.The method for preparing the dithiocarbamic acid an alkali metal salt comprises the reaction of amine, dithiocarbonic anhydride and alkali metal hydroxide.Normally reactant is mixed the low temperature reaction down that is incorporated between for example about 0 ℃ to 15 ℃.In one embodiment, be that the aqueous solution with amine is cooled to 0 ℃-15 ℃, drip dithiocarbonic anhydride again, dripping generally is to carry out before adding alkali metal hydroxide or during the course in inert atmosphere.In another embodiment, after the amine aqueous solution cooling, add alkali metal hydroxide, add dithiocarbonic anhydride subsequently.When all reactants mix under 0 ℃-15 ℃ low temperature, can be with mixture heat to envrionment temperature and stirring.

Dithiocar-bamate with the above-mentioned steps preparation is reacted (sulphur intermediate such as above-mentioned) with the sulphur intermediate usually immediately.Can use solvent so that react, alcohol is the solvent that relatively drips meaning.The reaction of sulphur intermediate and dithiocar-bamate is normally carried out between mixture refluxes in envrionment temperature.Autoreaction begins to finishing common about 5-of needs about 24 hours.After reaction finishes, water phase separated, product reclaims from solvent phase.

Behind single halogenation sulphur and the olefine reaction again with the product of dithiocar-bamate reaction product mixture normally, available formula V or formula V-A representative.When replacing alkene to react with aldehydes or ketones, reaction product also is a mixture, and primary product wherein believes it is the compound of formula V-B representative.

The also available method preparation that comprises the following steps of the dithiocar-bamate of sulphur coupling:

(A) with alkene and halogen reaction, obtain a halogenous intermediate,

(B) with intermediate and alkali metalsulphide and dithiocar-bamate reaction, the latter's amount should be enough to replace the halogen group that part is present in dithiocarbamate groups and/or partly is present in the sulfide base.

Any above-mentioned alkene and dithiocar-bamate all can be used in the method.The reaction of halogen and alkene is that prior art can be known, and it all is utilizable that halogen and alkene react any method that generates halogen-containing intermediate.

The alkali metalsulphide that was used for for second step is often with following structural formula representative:

M ₂S _x

(M is a basic metal in the formula, and X is 1,2 or 3, preferably with uranium sulfide as alkali metalsulphide, because its is economical and effectively.

In a specific embodiment, halogen-containing intermediate at first with alkali metalsulphide reaction, again with the reactant salt of dithiocarbamic acid.Though above-mentioned reactant can different ratios react, usually wish 4 normal halogen-containing intermediates and 1 mole alkali metalsulphide and 2 moles dithiocar-bamate are reacted.Temperature of reaction can be any temperature easily, as in some instances from envrionment temperature to about 100 ℃ or higher temperature.The product that this reaction obtains generally is a mixture, mainly comprises the dithiocarbamate that is used for lubricating oil and the coupling of functional liquid sulphur.

The preparation of sulfuration high alkalinity product:

The preparation of sulfuration high alkalinity product of the present invention is that high alkalinity product (A) or boracic high alkalinity product (A ') are contacted one effective period with sulphur or sulphur source (B) under enough temperature, to form required sulfur product.As noted above, believe that it is thiosulphate that sulfur product has part.The carrying out of contact can mix with the standard hybrid technology sulphur or sulphur source with the high alkalinity product.Generally be at about 0.1-about 200 hours duration of contact, be about 30 hours of about 10-in some instances, temperature generally is a room temperature to the reactant decomposition temperature or to the decomposition temperature of the product that lowest decomposition temperature is arranged, preferably about 20 ℃-Yue 300 ℃, be more preferably about 20 ℃-200 ℃, particularly about 20 ℃-Yue 150 ℃.Generally, the equivalent ratio in the sulphur of every normal high alkalinity product or sulphur source is that about 0.1-is about 10, and preferably about 0.3-is about 5, particularly about 0.5-about 1.5.Be whenever amount high-alkali product about 0.65-about 1.2 normal sulphur or sulphur source in one embodiment.

Be the reaction purpose, the sulphur of monovalent or sulphur source (B) are based on to be provided and high alkalinity product (A) or the middle SO of boracic high alkalinity product (A ') ₂The mole number of the sulphur of reaction.Therefore, for example the monovalent of elementary sulfur heavily equals its nucleidic mass.SO in the high alkalinity product that provides with reaction of Salmon-Saxl is provided for the high alkalinity product (A) of monovalent or boracic high alkalinity product (A ') ₂Mole number.Therefore, contain 1 mole of SO ₂High alkalinity product (A) or the equivalent of boracic high alkalinity product (A ') equal its actual weight.Contain 2 moles of SO ₂The equivalent of high alkalinity product equals half of its actual weight.

We do not wish to be limited by theory, and believe SO ₂Or SO ₂The source is as acid material (A) (V) or use SO ₂Or SO ₂The source formed product of displacement acid material (A) (V) is many mixture of products, but comprises the sulfide to small part; And the product that forms as the result with sulphur or sulphur source (B) sulfuration also is many mixture of products, but comprises the thiosulphate of part at least.For example, use CO as high alkalinity product (A) ₂As the sodium sulfonate of acid material preparation, then it is representative with the following formula:

RSO ₂Na(N _A2CO ₃) _xHigh alkaline azochlorosulfonate acid sodium

With this sodium sulfonate and SO ₂Or SO ₂The sulfide that the source contact forms can be represented by following formula:

RSO ₃Na(N _A2SO ₃) _xSulfide

Carrying out thiosulphate that sulfuration forms with sulfide and sulphur or sulphur source (B) can the following formula representative:

RSO ₃Na（N _a2S ₂O ₃） _x

Above-mentioned x in various generally is 1 or bigger number, and the available infrared or radix analysis of progress of these two reactions is measured.The technology that quantitative assay the present invention vulcanizes the sulfide of high alkalinity product or thiosulfate levels is with known differential pulse polarography in the analytical technology, comprises mensuration electric current/the impose on electromotive force relation of the sample in the electrolyzer.

The preparation that following example 1-13 explanation the present invention vulcanizes the high alkalinity product.

Example 1

With the 1400g(5.5 equivalent) first sulfide and sulphur content from example A-1 be 12.6%(weight), sodium content is 17.6%(weight) SO ₂, the 300g(1.0 equivalent) be 10.7%(weight from second sulfide and the sulphur content of example A-1 product), sodium content is 16.2%(weight) SO ₂The mixture heating up to 140 of sulphur and 208g(6.5 equivalent) ℃, and stir and kept this temperature 22 hours, so that 1535 required products to be provided, be brown oily.The sulphur content of product is a 22%(weight), sodium content is a 16.9%(weight).

Example 2

With the 1172g(4 equivalent) example A-47 product and 64g(2 equivalent) mixture heating up of sulphur is to 140-150 ℃, and stir, remained on this temperature 21 hours, obtain the required product of 1121g, be brown oily.The sulphur content of product is a 15.7%(weight), sodium content is a 17.2%(weight).

Example 3

With the 1172g(4 equivalent) example A-47 product and 102g(3.2 equivalent) mixture heating up of sulphur is to 140-150 ℃, and stir and kept this temperature 21 hours, obtain the required product of 1246g, be brown oily.Product sulfur-bearing 17.5%(weight), contain sodium 16.6%(weight).

Example 4

With the 1464g(6 equivalent) example A-47 product and 125g(3.9 equivalent) mixture heating up to 135 ℃ of sulphur, and stir, kept this temperature 23 hours.The mixture diatomite filtration obtains the required product of 1430g.

Example 5

500gA-47 product and 77g sulphur mixture heating up to 149-153 ℃, and are stirred, kept this temperature 23 hours, obtain the required product of 472g.

Example 6

With the 880g(2 equivalent) example A-49 product and 77g sulphur (2.4 equivalent) is heated to 130 ℃, stirs to keep this temperature 17.5 hours.Add the 100g thinning oil.Reaction mixture is heated to 140-150 ℃ and stirred 1 hour, and filtering mixt obtains the required product of 985g, is brown oily.Product sulfur-bearing 12.1%(weight), contain sodium 10.48%(weight), boracic 5.0%(weight).

Example 7

With the 1310g(3.36 equivalent) example A-48 product and 53.4g(1.67 equivalent) mixture heating up of sulphur is to 140-150 ℃, and keep this temperature to stir 29.5 hours.Reaction mixture is chilled to 100 ℃, uses diatomite filtration, obtains the required product of 1182g, is the brownish black oily.Product sulfur-bearing 12.0%(weight), uranium-bearing 17.5%(weight), base number (bromic acid indigo plant) 241.The copper strip test evaluation (AST M D 130) of product is 1B-2A(100 ℃, 3 hours, and 1%) and 2A-2B(100 ℃, 3 hours, 5%).

Example 8

With the 1500g(3.84 equivalent) example A-48 product and 98.4g(3.10 equivalent) mixture heating up to 150 ℃ of sulphur, under nitrogen blanket, keep this temperature to stir 24 hours.Use the diatomite filtration mixture, obtain the required product of 1418g.Product sulfur-bearing 14.0%(weight), contain sodium 16.6%(weight), base number (bromic acid indigo plant) is 150.The copper strip test evaluation (ASTM D 130) of product is 2B-2C(100 ℃, 3 hours, and 1%) and 4B(100 ℃, 3 hours, 5%).

Example 9

With the 8960g(70 equivalent) example A-1 product and 1024g(32 equivalent) sulphur mixture heating up to 140-150 ℃ and stir be blown into mixture 2240g(70 equivalent) SO ₂, speed 1.5cfh lasts 34 hours.Reaction mixture blew 1 hour with nitrogen in 150 ℃, and diatomite filtration obtains the required product of 9330g, is bright brown oily.Its sulphur content is a 21.68%(weight), containing the sodium amount is 15.86%(weight), copper strip test evaluation (ASTM D 130) is 1A(100 ℃, 3 hours, and 5%).

Example 10

With the 1468g(4 equivalent) example A-50 product and 128g(4 equivalent) mixture heating up to 140 ℃ of sulphur, and keep this temperature to stir 1.5-2 hour, and obtain the required product of 1488g, be brown oily.Product sulfur-bearing 16.0%(weight), contain sodium 11.8%(weight).

Example 11

With the 1222g(3.33 equivalent) example A-50 product and 80g(2.5 equivalent) mixture of sulphur is heated to 140 ℃ under nitrogen, and stir simultaneously, and remained on this temperature 2-3 hour.With the diatomite filtration reaction mixture, get the required product of 1150g, be brown oily.Product sulfur-bearing 14.4%(weight), contain sodium 11.9%(weight).

Example 12

With the 3480g(20 equivalent) product and the 320g(10 equivalent of example A-43) sulphur be blown into the 640g(20 equivalent 140-150 ℃ of speed with 1.5cfh) SO ₂Use N ₂Purge reaction mixture, diatomite filtration obtains the required product of 3728g, is brown oily.Product sulfur-bearing 15.9%(weight), contain sodium 11.3%(weight).

Example 13

With the 336g(0.5 equivalent) the 1 equivalent product deutero-high alkalinity sulfurated lime of example A-2.1 normal SO ₂With the 16g(0.5 equivalent) mixture heating up to 135 of sulphur ℃, kept 8 hours, and then kept 6 hours to 150 ℃.Use the diatomite filtration mixture, obtain the required product of 255g.Product calcic 12.1%(weight), sulfur-bearing 5.7%(weight).

The active sulphur reduction:

In a specific embodiments, the high-alkali product of sulfuration of the present invention contacts to reduce the active sulphur content of this type of product with at least a active sulphur reductive agent of significant quantity.This being reduced in when sulfurized high alkalinity product is considered to that required application had big corrodibility used.The meaning of " active sulphur " speech is the sulphur form that copper or similar substance are caused stain.The activity that can be used for measuring sulphur as the standard test of ASTM D 130 and so on.

The active sulphur reductive agent can be air and gac, steam, above-mentioned small tenon is entitled as the one or more boron compounds (for example boric acid) under " the high alkali product of boracic (A ') ", and one or more phosphides under the above-mentioned subhead " phosphoric acid (A) (I) (C) " (for example phosphorous acid two-and tributyl ester, triphenyl phosphite) or above-mentioned small tenon are entitled as one or more alkene under " as the olefine sulfide in sulphur source (B) " (C for example _16-18The alpha-olefin mixture), the combination of " as the sulfurized Diels-Alder adduct in sulphur source (B) " or " as the sulfuration terpenes in sulphur source (B) ".

In a specific embodiments, the active sulphur reductive agent be above-mentioned subhead " carboxylic acid (A) (I) (a) one or more carboxylic acid or derivatives thereofs and one or more such as amine nitrogenous compound or such as the reaction product of phenol or pure organic hydroxy compounds.Maleic anhydride and polyisobutenyl (Mn=700-2000) succinyl oxide is particularly preferred carboxylic acid.The amine that is fit to is disclosed in D.S.P.4, and the 234,435, the 21st hurdle the 4th walks to the 27th hurdle the 50th row; The alcohol that is fit to is disclosed in the 28th hurdle the 63rd and walks to the 35th hurdle the 54th row.The reaction product of carboxylic acid or derivative and nitrogenous compound or oxy-compound can be with one or more above-mentioned nitrogenous compounds and/or one or more.U.S.P.4,234,435 the 41st hurdles 48 walk to the 42nd hurdle 17 disclosed post-treatment agents of row (for example boric acid) and carry out aftertreatment.The step and the USP4 that prepare the reaction product and the aftertreatment reaction product of these carboxylic acids, 234,435 the 27th hurdle 51 walks to the 28th hurdle 62 row; 35 hurdles 55 walk to 36 hurdles, 33 row; 42 hurdle 18-52 are capable, and described method is identical.Necessary is with acylting agent in this patent of carboxylic acid-substituted disclosed by the invention or high-molecular weight acylting agent, generally uses equivalent.Now with USP4,234,435 aforementioned chapters and sections draw in this for reference.

In one embodiment, composition of the present invention is a lubricating composition or oil base official energy liquid.In this embodiment, the reduction of vulcanizing the active sulphur content of high alkalinity product is to mix the II family metal-salt that the above-mentioned small tenon of significant quantity is entitled as the one or more phosphorodithioic acid described in " phosphoric acid (A) (I) (C) " in the said composition, comprise the dicyclohexyl zinc dithiophosphate, the dioctyl zinc dithiophosphate, two heptan phenyl phosphorodithioic acid barium, dinonyl phosphorodithioic acid calcium, the zinc salt of thiophosphoric anhydride and the phosphorodithioic acid that waits mole Virahol and n-hexyl alcohol mixture reaction to obtain and the preferred zinc salt that reacts the phosphorodithioic acid that obtains by thiophosphoric anhydride and 60 moles of %4-methyl-2-amylalcohols and 40 moles of % isopropanol mixtures.Like this Pei Fang lubricating composition or sense liquid generally comprise can reach about 20%, preferred about 10%, particularly about 5%(weight) the dithiophosphates of above-mentioned second family metal.

The copper strip test of ASTM D 130 can be used to measure the present invention and vulcanizes active sulphur level in the high alkalinity product.Improved copper bar evaluation can be indicated the decreased extent of active sulphur and the possibility that corrosion reduces.

Sulfuration high alkalinity product is to carry out one effective period active sulphur content is reduced to the level that is enough to provide required copper bar rating under enough temperature with contacting of active sulphur reductive agent.Contact available standards hybrid technology with the active sulphur reductive agent with vulcanize the high alkalinity product and mix and carry out.Generally about 50 hours duration of contact at about 0.1-, about 30 hours of preferably about 1-, about 10 hours of about 1-commonly used.Temperature is generally about temperature to the reactant decomposition temperature or have the decomposition temperature of the product of lowest decomposition temperature, about 300 ℃ of preferably about 20-, about 180 ℃ of particularly about 120-.

Generally, activity reducing agent can reach about 1 with the weight ratio of sulfuration high alkalinity product, but preferably reaches about 0.5.In one embodiment, the active sulphur reductive agent is a boric acid, it is about 0.001-about 0.1 with the weight ratio of sulfuration high alkalinity product, preferred about 0.005-about 0.03, in another embodiment, the active sulphur reductive agent is one of above-mentioned phosphite, preferred triphenyl phosphite, and it is about 0.1-about 0.2 with the weight ratio of sulfuration high alkalinity product.In another embodiment, the active sulphur reductive agent is the alkene of having discussed on, and it is about 0.2-about 0.7 with the weight ratio of sulfuration high alkalinity product.

Following example 14-36 is that explanation prepares the method that the present invention vulcanizes the high alkalinity product with the active sulphur reductive agent.

Example 14-19

In example 14-19, press example, the product that method makes contacts with the boric acid of following indication amount, contacts 2 hours in 140-160 ℃ under nitrogen flushing.Mixture is through coupling vacuum stripping to 150 ℃, and diatomite filtration obtains required product, and products therefrom carries out ASTM D 130 copper strip tests (5%(weight), 3 hours, 100 ℃), the result is as follows:

ExampleH ₃BO ₃ ^* The copper bar evaluation

10????????????????????14.06?????????????4A

11?????????????????????7.01?????????????3A

12?????????????????????3.5??????????????2C

13?????????????????????1.8??????????????2A

14?????????????????????0.9??????????????1B

15?????????????????????0.4??????????????2B

1 ^**0 4B

^*With sulfuration high alkalinity product and H ₃BO ₃Gross weight be the H of basic calculation ₃BO ₃Weight percentage.

^*The product that example 1 obtains is tested as a comparison.

Example 20

With the 500g(2 equivalent) product and the 77g(2.4 equivalent that make by example A-47) mixture of sulphur is 140-155 ℃ of heating 23 hours down, stirs simultaneously, adds 289gC _16-18The alpha-olefin mixture.Mixture was 147-155 ℃ of following stirring heating 23 hours, and the copper bar of product evaluation (ASTM D 130) is 2C(5%, and 3 hours, 100 ℃)

Example 21

The 435g product that will make by example 1 and the mixture of 37.5g tributyl phosphate are in 100 ℃ of following stirring heating 6 hours, diatomite filtration mixture, the product sulfur-bearing 19.8%(weight that obtains), contain sodium 15.5%(weight), phosphorous 0.8%(weight).The copper bar evaluation (ASTM D 130) of product is 1A(5%, 3 hours, and 100 ℃)

Example 22

The product that 490g is made by example 1 and the mixture of 111g triphenyl phosphite were 100-110 ℃ of following stirring heating 6 hours, and nitrogen flushing speed is 0.1cfh.Use the diatomite filtration mixture, the product sulfur-bearing 17.4%(weight that obtains), phosphorous 1.8%(weight), contain sodium 13.75%(weight).

Example 23

A: with the 1683g(1.5 equivalent) mixture heating up of polyethylene diamines residue deutero-polyisobutenyl (Mn=950) succinimide and 495g thinning oil is to 80-90 ℃, add the 115g(4.5 equivalent) phosphoric acid, last 1 hour, reaction mixture be heated to 180-200 ℃ 3-4 hour to remove 65g water, be heated to then 210 ℃ 3 hours.The mixture diatomite filtration obtains the 2430g product, is brown oily.

B: the product that 293g is made by example 5 and the mixture heating up of 200ml toluene drip 29g by the product that A in this example makes to 60-70 ℃, last 1 hour.Reaction mixture refluxed heating 2 hours, vacuum are steamed and are desolventized.The mixture diatomite filtration obtains the 560g product, is brown oily, sulfur-bearing 8.35%(weight), phosphorous 2.8%(weight), contain sodium 8.46%(weight).

Example 24

With sulfur-bearing 19.8%(weight), contain sodium 15.7%(weight) be heated to 150 ℃, nitrogen flushing simultaneously, speed 1cfh by the 430g product of example 3 preparation.Reaction mixture is used steam bubbling 2.25 hours.Steam off is cooled to 100 ℃ with reaction mixture, adds 10g toluene.Heated mixt to 155 is ℃ 0.5 hour under vacuum, uses the diatomite filtration mixture, obtains the required product of 370g, and its copper bar evaluation (ASTM D 130) is 2E-3A(100 ℃, and 3 hours, 5%)

Example 25

With 1505g sulfur-bearing 19.8%(weight), contain sodium 15.7%(weight) press the product of example 3 preparation and the mixture heating up to 150 ℃ (nitrogen flushing speed 0.5cfh) of 15.1g gac.Blowing air bubble (flow rate 1.5cfh) is 3.75 hours in reaction mixture.Use the diatomite filtration mixture, obtain the required product of 1230g, its copper bar evaluation (ASTM D 130) is 2E(100 ℃, 3 hours, and 5%)

Example 26

With 100g sulfur-bearing 21.8%(weight) press the product and the commercially available C of 512g of example 5 preparation _16-18The mixture of alpha-olefin mixture be heated with stirring to 140-150 ℃ 32 hours.Product obtains the required product of 1430g with diatomite filtration, and its sulphur content is a 10.86%(weight), containing the sodium amount is 9.11%(weight), copper bar evaluation (ASTM D 130) is 1A(100 ℃, 3 hours, and 5%).

Example 27

With 435g sulfur-bearing 22%(weight), contain sodium 16.9%(weight) mixture of pressing the product of example 5 preparation and 29g dibutyl phosphite is in 100 ℃ of stirring heating 5 hours.The product diatomite filtration obtains the required product of 415g, sulfur-bearing 18.15%(weight), contain sodium 15.38%(weight), phosphorous 1.0(weight), copper bar evaluation (ASTM D 130) 1A(100 ℃, 3 hours, 5%).

Example 28

With 867g sulfur-bearing 22.3(weight), contain sodium 15.5%(weight) press the product of example 5 preparation and 145g diester and commercially available C derived from maleic anhydride ₈-C ₁₀The mixture of alcohol mixture was in 150 ℃ of stirring heating 8-10 hours.Use diatomite filtration, obtain the required product of 989g, sulfur-bearing 19.7%(weight), contain sodium 13.6%(weight), copper bar evaluation (ASTM D 130) 2B(100 ℃, 3 hours, 5%).

Example 29

With the high-alkali Sulfothiorine of 282g (simultaneously with 1 equivalent example A-1 product and 1 equivalent SO ₂Carry out prepared in reaction with 0.5 equivalent elementary sulfur) and 115.8g react with polybutene (Mn=950) succinyl oxide and polyvinylamine, the mixture of the product that makes with the boric acid aftertreatment be heated with stirring to 150 ℃ 3 hours.Use the diatomite filtration mixture, obtain the 340g product, be brown oily.The copper bar evaluation (ASTM D 130) of product is 3A(100 ℃, 3 hours, and 5%).

Example 30

With 268g high alkalinity Sulfothiorine (simultaneously with 1 equivalent example A-1 product and 1 equivalent SO ₂Carry out prepared in reaction with 0.5 equivalent elementary sulfur) and the mixture of products that makes with the reaction of polybutene (Mn=950) succinyl oxide and polyvinylamine of 112g be heated with stirring to 150 ℃ 3 hours.Use the diatomite filtration mixture, obtain the 310g product, be brown oily, its copper bar is assessed as 313(100 ℃, and 3 hours, 5%).

Example 31

With the 268g(1 equivalent) high alkalinity Sulfothiorine (uses 1 equivalent example A-1 product and 1 equivalent SO simultaneously ₂With 0.5 equivalent elementary sulfur prepared in reaction), the 76g(0.2 equivalent) product of maleic anhydride and oleylamide reaction and 100ml dimethylbenzene be blended under the nitrogen blanket stirring heating 150-160 ℃ 3-4 hour.Vacuum is steamed the solvent that removes in the reaction mixture, under agitation adds 50g100 neutral oil.The mixture diatomite filtration obtains the 330g product, is brown oily.The copper bar evaluation (ASTM D 130) of product is 1A(100 ℃, 3 hours, and 5%).

Example 32

134g high alkalinity Sulfothiorine (is used 1 equivalent example A-1 product and 1 equivalent SO simultaneously ₂With 0.5 equivalent elementary sulfur prepared in reaction), the mixture of the reactor product of 134g maleic anhydride and oleylamide and 50ml dimethylbenzene be heated with stirring to 140-150 ℃ 4 hours, vacuum is steamed and to be desolventized.The mixture diatomite filtration obtains the brown oily product of 100g, and copper bar evaluation (ASTM D 130) is 1B(100 ℃, and 3 hours, 5%).

Example 33

882g high alkalinity Sulfothiorine (is used 1 equivalent example A-1 product and 1 equivalent SO simultaneously ₂With 0.4 equivalent elementary sulfur prepared in reaction), the product of handling with oleylamide behind the hydroxyl thioether of 235g maleic anhydride and uncle's lauryl mercaptan and the propylene oxide reaction and the mixture of 200ml dimethylbenzene be heated with stirring to 150-160 ℃ 3 hours.Vacuum is steamed and is desolventized, and the mixture diatomite filtration obtains the brown oily product of 640g, and copper bar evaluation (ASTM D 130) is 1A(100 ℃, and 3 hours, 5%).

Example 34

With 1029g high alkalinity Sulfothiorine (simultaneously with 1 equivalent example A-1 product and 1 equivalent SO ₂With 0.4 equivalent elementary sulfur prepared in reaction), 235g maleic anhydride and Ethomeen S/12(Armak product are accredited as two (2-hydroxyethyl) soybean amine) 1: 1 molar reactive product and the mixture of 200ml dimethylbenzene be heated with stirring to 150-160 ℃ 3-4 hour.Vacuum is steamed and is desolventized, and diatomite filtration obtains the brown product of 1040g pasty state, and copper bar evaluation (ASTM D 130) is 2B(100 ℃, and 3 hours, 5%).

Example 35

With 1029g high alkalinity Sulfothiorine (simultaneously with 1 equivalent example A-1 product and 1 equivalent SO ₂With 0.4 equivalent elementary sulfur prepared in reaction), 270g maleic anhydride and 2 ethyl hexylamine (mol ratio 1: 1) reaction, use again the mixture of the product of dodecyl benzo diazole (mol ratio 1: 1) aftertreatment preparation and 200ml toluene be heated with stirring to 150-160 ℃ 3-4 hour.Vacuum is steamed and is desolventized, and the mixture diatomite filtration obtains the brown oily product of 1148g, and copper bar evaluation (ASTM D 130) is 1A(100 ℃, and 3 hours, 5%).

Example 36

With 1029g high alkalinity Sulfothiorine (simultaneously with 1 equivalent example A-1 product and 1 equivalent SO ₂With 0.4 equivalent elementary sulfur prepared in reaction), 250g maleic anhydride and Propomeen(Azko product are accredited as two (2-hydroxypropyl) fat amine) with the mixture of the product of 1: 1 molar ratio reaction and 200ml dimethylbenzene be heated with stirring to 150-160 ℃ 3-4 hour.With the mixture diatomite filtration, obtain the brown oily product of 1090g, its copper bar evaluation (ASTM D 130) 1A(100 ℃, 3 hours, 5%).

Sulfuration high alkalinity product/unvulcanised boracic high alkalinity product combination

When sulfuration high alkalinity product prepared with high alkalinity product (A), the present composition also can comprise at least a unvulcanised boracic high alkalinity product.Unvulcanised boracic high alkalinity product can be above-mentioned any boracic high alkalinity product (A ').The mixing step preparation of these composition available standards.The weight ratio of unvulcanised boracic high alkalinity product and sulfuration high alkalinity product is preferably in about 20: 1 scope, and preferred about 10: 1, particularly 5: 1.In a specific embodiments, this ratio is about 20: 1 to about 1: 20, and preferred about 10: 1 to about 1: 10, more preferably about 5: 1 to about 1: 5, particularly about 2: 1 to 1: 2, best was about 1: 1.

Mixing time is generally several seconds to about 20 hours.Mixing temperature is generally about room temperature to the decomposition temperature of reactant or the decomposition temperature of the desired product of lowest decomposition temperature is arranged, preferably about 20 ℃ to about 150 ℃.These components generally are to mix in the process of preparation enriched material, lubricant or sense liquid, will discuss in more detail below.

Following example has illustrated sulfuration high alkalinity product of the present invention/unvulcanised boracic high alkalinity product combination.

Example 37

Following composition is mixed under temperature:

Example 5 products 50 Wt.%

Example A-44 product 50 Wt.%

It is as the additive of conventional liquid fuel, lubricant and sense liquid that the present invention vulcanizes high alkali composition.The lubricant and the sense liquid of the high alkali composition of Containing Sulfur of the present invention present improved EP, wear-resistant and/or antioxidant properties.Fuel presents improved wear-resistant and/or antioxidant property.Sense liquid can be oil base or water base.

The oil base concentrated solution, lubricating composition and oil base official energy liquid:

Oil lubricant of the present invention and sense liquid composition are based on the various oil of lubricant viscosity, comprise natural and complete become lubricating oil and their mixture.Lubricating composition can be lubricating oil and the fat that is used for industry and motor car engine, transmission case and axle.Containing these lubricating compositions that the present invention vulcanizes high alkali composition all is effective in many application, the base chamber lubricating oil that comprises spark ignition and ignition, engine comprises automobile or motortruck engine, two-cycle engine, aviation piston engine, peculiar to vessel and underload diesel engine etc.Automatic transmission liquid, transmission shaft (transaxle) lubricant, gear lubricant, metal working lubricant, hydraulic efficiency oil and other lubricating oil and oil/fat composition all can be improved because of adding the present invention vulcanizes the high alkalinity product.Lubricating composition is effective especially as gear oil, and sense liquid is effective especially as cutting oil.

The oil that degree of lubrication is arranged that lubricant of the present invention and sense liquid composition adopt normally exists with main amount (promptly greater than 50wt% amount), about 60wt% of composition preferably, or greater than about 70% or 80%(weight of composition).Have in the embodiment one, it is measured greater than about 90wt%.

In one embodiment, sulfuration high alkalinity product of the present invention is used for gear oil, and can avoid using other phosphorous extreme pressure and/or anti-wear agent.This gear oil composition general phosphorous be lower than about 0.5%, be lower than about 0.25% or be lower than about 0.1%(weight); Be lower than about 0.05%(weight in one embodiment).

In one embodiment, select the oil of degree of lubrication to be arranged to provide kinetic viscosity at least about 3.5 or at least about 4.0CSt(100 ℃) lubricating composition.In one embodiment, the oil of selecting to have lubricant viscosity is about 60 or about 65 so that SAE gear oil viscosity number to be provided at least, preferably the lubricating oil composition of about SAE75.Lubricating oil composition also can have so-called multistage evaluation, as SAE60W-80, and 65W-80,65W-90,75W-80,75W-90,80W-90,80W-140 or 85W-140.Multistage lubricant can comprise the in a small amount viscosity modifier of viscosity modified amount, and it is so that above-mentioned lubricated grade to be provided with the oil preparation that degree of lubrication is arranged.Useful viscosity modifier comprises polyolefine, as polybutene; Rubber is as phenylethylene/butadiene or styrene/isoprene rubber or polyacrylic ester, as polymethacrylate.Useful commercially available viscosity modifier comprises Rohm ﹠amp; The acrylic acid or the like viscosity modifier that Haas provides, the Lubrizol 3174 that Shellvis rubber that Shell Chemieal provides and Lubrizol Corp provide.

In another embodiment, select the oil of lubricant viscosity is arranged to be provided for the lubricating composition of crankcase, as the crankcase in gasoline and the diesel engine.In general, selecting lubricating composition is 10W so that SAE crankcase viscosity number to be provided, the lubricating oil of 20W or 30W grade.Lubricating composition also can have so-called multistage evaluation, as SAE10W-30, and 10W-40,10W-50 etc.As mentioned above, multigrade lubricating oil comprises that the viscosity modifier of preparing with the oil that lubricant viscosity is arranged is to provide above-mentioned lubricated grade.

In general, lubricant of the present invention and sense liquid contain a certain amount of the present invention and vulcanize the high alkalinity product, and this amount is enough to provide and has desired properties, as the lubricant and the sense liquid of improved anti-oxidant, extreme pressure, thermally-stabilised and/or abrasion resistance.Usually, the amount of this additive is that about 0.01-of lubricant or sense liquid gross weight is to about 20%.In one embodiment, the amount of vulcanizing high-alkali product be lubricating composition or sense composition about 0.5% or about 1% or about 2% to about 10% about 8% or 7%(weight).In the lubricating oil composition of utmost point unfavourable condition operation, as the boat diesel engine lubricating composition, the amount of the high-alkali product of sulfuration of the present invention can reach about 30%(weight of lubricating composition gross weight) or higher.

The present invention can directly add lubricant as vulcanizing high-alkali product, sense liquid and fuel, and perhaps their available organic solvent inert/thinner basically such as petroleum naphthas, benzene, dimethylbenzene or above-mentioned common liquid fuel dilute the formation multifunctional additive for lubricating oils.This class enriched material generally contain have an appointment 0.01% about 1% or about 5% or about 10%(weight) to about 70% about 80% or about 90%(weight) this vulcanize high-alkali product, also can contain one or more other conventional additives known in the art or as herein described.

In one embodiment, vulcanize high-alkali product and be used for the metal working operation.The metal working operation comprises cutting and forming operation.Cutting operation comprises brill, attacks, draws, dashes, grinds, and that forming operation comprises is curved, forge, roll, press.Operation is to be used for ferrous metal or non-ferrous metal.The example of metal and alloy comprises steel, copper, aluminium, brass, bronze and titanium.Generally, the consumption of high-alkali product be the metal working lubricant about 1% or about 2% or about 3% to about 20% 15% or 10% or 8%(weight).The metal working lubricant contains the oil that lubricant viscosity is arranged, and normally contains low viscosity mineral oil, for example dynamic viscosity reach about 5 or about 4.5CSt(100 ℃) oil.The metal working base fluid comprises the above-mentioned oil that lubricant viscosity is arranged.In one embodiment, the oil that lubricant viscosity is arranged is 100 neutral or 200 neutrality, preferably 100 neutral base oils.

Natural oil and synthetic oil:

The natural oil for preparing lubricating oil of the present invention and sense liquid comprises animal oil or vegetables oil (for example Viscotrol C and lard) and mineral lubricating oils, as liquid petroleum and solvent treatment or acid-treated paraffinic hydrocarbon, naphthenic hydrocarbon or blended paraffin/naphthenic hydrocarbon type.The oil that lubricant viscosity is arranged that derives from coal or resinous shale also is suitable for.Ucon oil comprises the alkene (for example polybutene, polypropylene, propylene/isobutylene copolymers, chlorinated polybutylenes etc.) of hydrocarbon ils and halo hydrocarbon ils such as polymeric and copolymerization; Poly-(1-hexene), poly-(the hot hydrocarbon of 1-), poly-(1-dodecylene) etc. and their mixture; Alkylbenzene (for example dodecylbenzene, four decyl benzene, dinonyl benzene, two (α-ethylhexyl) benzene etc.); Many benzene (for example hexichol, triphen, the many benzene of alkylation etc.); Alkylation phenyl ether and alkylation diphenyl sulfide and their derivative, congener and homologue etc.

By terminal hydroxy group esterified, etherification modified alkylene oxide polymer and multipolymer and its derivative constituted another kind of operable known ucon oil.This can be by the polymerization by the ethylene oxide or third alkylene oxide, (for example molecular-weight average is about methyl-poly-Isopropanediol ether of 1000 to the oily institute illustration of the alkyl of these polyoxyalkylene polymers and aryl ethers preparation, molecular weight is about the polyoxyethylene glycol phenyl ether of 500-1000, molecular weight is about the polypropylene glycol diethyl ether of 1000-1500 etc.) or their monobasic and multi-carboxylate, for example acetic ester, mixed C _3-8The C of fatty acid ester or TEG ₁₃The oxygen acid diesters.

Another kind of operable suitable ucon oil comprises ester (phthalic acid for example, succsinic acid, alkyl succinic acid, the alkenyl succinic acid of dicarboxylic acid, toxilic acid, nonane diacid, suberic acid, sebacic acid, fumaric acid, hexanodioic acid, linoleic acid dimer, propanedioic acid, (employed alcohol is butanols for example for the ester that thiazolinyl propanedioic acid and all kinds of alcohol form, hexanol, dodecanol, α ethylhexyl alcohol, ethylene glycol, Diethylene Glycol monoether, propylene glycol etc.).The object lesson of these esters comprises Polycizer W 260, the sebacic acid ethylhexyl, the just own ester of fumaric acid two, dioctyl sebacate, diisooctyl azelate, two different decayl esters of azelaic acid, didecyl phthalate, sebacic acid two (eicosyl) ester, the ethylhexyl of linoleic acid dimer, one mole of sebacic acid and two moles of TEGs and two moles of α-thylhexoic acid reactions form complex ester and analogue.

Ester as synthetic oil also comprises those C ₅-C ₁₂Esters that monobasic carboxylic ester and many alcohol form and as neopentyl glycol, propane three methyl alcohol, tetramethylolmethane, Dipentaerythritol, the polyol ester of tripentaerythritol etc.

As poly-alkyl one, poly-aryl-, poly-alkoxyl group-or poly-aryloxy silicone oil and silicon ester comprise another kind of ucon oil (tetraethyl orthosilicate for example, silicic acid four isopropyl esters, silicic acid four α-ethylhexyl, silicic acid four (the own ester of 4-methyl), silicic acid four (to tertiary butyl phenyl ester), hexyl-(4-methyl-α-pentyloxy) sily oxide, polymethyl siloxane, PSI etc.).Other ucon oil comprises the liquid ester (for example Tritolyl Phosphate, trioctyl phosphate, decane diethyl phosphoric acid etc.) of phosphoric acid, polymeric tetrahydrofuran (THF) and analogue.

Unpurified, the purified of the above-mentioned type, the oil of re-refining, natural or synthetic (and their two or mixture of three kind) can both be used for lubricant of the present invention.Unpurified oil be direct must be by the oil without purification process of natural or synthetic source.For example, the direct shale oil that obtains of destructive distillation, the oil oil that directly obtains from single flash or be unrefined oil from 2 sections ester oils that directly obtain of esterification and without further handling.Treated oil is similar to unrefined oil, and just they are handled to improve their one or more performances through further in one or more step purifying.For the art technology expert, many such purification techniques are known, as solvent extraction, and second distillation, soda acid extracts, and filters diafiltration etc.Producing of rerefined oils is similar to the working method of producing the treated oil that is put to use.This type of rerefined oils be also referred to as recovered oil or reprocessed oils and often be with for remove with after the additive or the technology processing of oil fracture product.

Metal deactivator

In one embodiment, the high-alkali product of sulfuration of the present invention is used in combination with at least a metal deactivator.In this embodiment, the amount of metal deactivator in lubricant of the present invention or sense liquid composition is enough to provide metal deactivation effect, and the level of its amount reaches the about 20% of lubricant or sense total amount of liquid, preferably about 10%(weight).Usually the level of metal deactivatorization reach lubricating oil or sense total amount of liquid about 2% about 1% or about 0.5%(weight).

Metal deactivator used herein can reduce metallic corrosion, and as the corrosion of copper, metal deactivator also claims metal passivator.These metal deactivators generally are nitrogen and/or sulfur heterocyclic compound, as dimercaptothiodiazole, and triazole, amino mercapto thiadiazoles, imidazoles, thiazole, tetrazolium, hydroxyquinoline oxazoline, tetrahydroglyoxaline, thiophene, indoles, indazole, quinoline, benzoxazine, dithiol ， oxazole ， oxatriazole, pyridine, piperazine, triazine and their one or more derivatives.Metal deactivator preferably includes at least one and can be substituted or unsubstituted triazole.The example of the compound that is fit to has benzotriazole, alkyl substituted benzene and triazole (tolytriazole for example, the ethyl benzotriazole, the hexyl benzotriazole, octyl group benzotriazole etc.) and alkaryl or the aralkyl benzotriazole and the hydroxyl that replace, alkoxyl group, halogen (particularly chlorine), nitro, the replacement benzotriazole that carbon oxygen base and carbonyl alkoxyl group replace.Preferred triazole is benzotriazole or contains the 1 alkyl benzotriazole to the alkyl of about 20 carbon atoms that preferred alkyl contains 1 to about 8 carbon atoms.Benzotriazole and tolyl-triazole are useful.

In a specific embodiments, metal deactivator is the product of dispersion agent and dimercaptothiodiazole reaction.Dispersion agent generally is that reaction product with carboxylic acid and amine and/or alcohol is a feature.These reaction product are generally used for lubricated field as dispersion agent, and usually are generically and collectively referred to as dispersion agent, although they can have other purposes except making dispersion agent.Carboxylic dispersants comprises succinimide dispersants, ester type dispersion agent and analogue.Succinimide dispersants normally polyamines and alkenyl succinyl oxide or acid-respons obtains; Ester type dispersion agent is the reaction product of alkenyl succinyl oxide or acid and alkylol cpd more than, and this reaction product can further use amine (as polyamines) to handle.Useful dispersion agent is disclosed in US.3, in 219,666 and US4,234,435, at this as a reference.Useful dispersion agent also comprises the ashless dispersant of following title for being discussed in " washing composition and dispersion agent ".Usually, be reflected between dispersion agent and dimercaptothiodiazole and take place, be with the two mixing and be heated above about 100 ℃.US4, this dispersion agents of 140,643 and US4,136,043 narrations react the compound that makes with dimercaptothiodiazole.Above-mentioned patent at this with its disclosed dispersion agent, dimercaptothiodiazole, the product that reaction method of the two and this reaction obtain as a reference.

In one embodiment, metal deactivator is the reaction product of phenol and aldehyde and dihydroxyl thiadiazoles.Used phenol is an alkylphenol preferably, and alkyl wherein contains about 6 at least, preferred 6 to about 24, preferably about 6 or about 7 to about 12 carbon atoms.Used aldehyde preferably contains 1 aldehyde to about 7 carbon atoms, and as formaldehyde, preferred aldehyde is formaldehyde or Paraformaldehyde 96.Aldehyde, phenol and dihydroxyl thiadiazoles generally are to reach about 150 ℃, preferred about 50 ℃ of hybrid reactions to about 130 ℃ temperature.Its mol ratio is every mole of about 2 moles of phenol of the about 0.5-of dihydroxyl thiadiazoles and the about 2 moles of aldehyde of about 0.5-.Preferably with three kinds of reagent equimolar amount reactions.

In one embodiment, metal deactivator is two (alkyl two sulphur) thiadiazoles.Preferably each alkyl is respectively done for oneself and is contained the alkyl of about 24 carbon atoms of 6-, aryl or aralkyl.Each alkyl can be respectively uncle's octyl group, nonyl, decyl, dodecyl or ethylhexyl.Metal deactivator can be two-2, uncle's 5-octyl group-two sulphur-1,3, and 4-thiadiazoles or itself and uncle's 2-octyl group-sulphur-5-sulfydryl-1,3, the mixture of 4-thiadiazoles, these materials are provided by Amoco Chemical Company with trade(brand)name Amoco 150.These two sulphur thiadiazole compounds are open as component (B), at this with the disulfide group thiadiazole compound openly as a reference with PCT bulletin WO88/03551.

Metal deactivator also can be the reaction product of benzotriazole and at least a amine.Used amine can be one or more monoamines or polyamines.These monoamines or polyamine can be primary amine, secondary amine or tertiary amine.Useful amine comprises US4, and 234,435 the 21st hurdles the 4th walk to the disclosed amine of the 27th hurdle the 50th row, at this as a reference.

Monoamine generally contains 1 to about 24 carbon atoms, and preferred 1 to about 12 carbon atoms, and preferably 1 to about 6 carbon atoms.Be used for monoamine example of the present invention and comprise methylamine, ethamine, propylamine, butylamine, octylame and amino dodecane.The example of secondary amine comprises dimethylamine, diethylamine, dipropyl amine, dibutylamine, methyl butyl amine, DEHA etc.Three grades of tertiary amines comprise Trimethylamine 99, Tributylamine, methyl diethylamide, N-Ethyldibutylamine etc.

Polyamine can be a fat, ring grease, heterocycle or aromatic amine.The example of polyamine comprises alkylidene group polyamine and heterocycle polyamine.The alkylidene group polyamine can be represented with following formula:

The mean value of n is between about 1-about 10 in the formula, and preferably about 2-is about 7, and " alkylidene group " base contains 1 to about 10 carbon atoms, about 6 carbon atoms of preferably about 2-; R replaces fatty group for the fat or the hydroxyl that can reach about 30 carbon atoms.These alkylene polyamines comprise the methylene radical polyamines, ethylidene polyamines, butylidene polyamines, propylidene polyamines, pentylidene polyamines etc.Also comprise higher homologue and relevant heterocyclic amine such as piperazine, the piperazine that N-amino-alkyl replaces.The specific examples of this class polyamines is a quadrol, diethylenetriamine, three (2-aminoethyl) amine, trimethylene diamine, trimethylene diamines, tri propylidene tetramine, tetracthylene pentamine, six ethylidene, seven amine, penten.

The higher homologue that two or more above-mentioned alkylene amine condensations are obtained is the similar use that is mixed with to two or more above-mentioned polyamines.

As above-mentioned ethylidene polyamine is useful polyamine.This type of polyamines is specified in Kirk Othmer work " Encyclopedia of Chemical Technology " second edition, Vol.7, PP22-37, Interscience Publishers, New York(1965).This class polyamines can be easily by 1,2-ethylene dichloride and ammonia react or by ethylenimine and a ring opening agent such as prepared in reaction such as water, ammonia.Reaction result has obtained comprising the complex mixture of the polyalkylene polyamine of cyclic condensation product such as piperazine and so on.Ethylidene polyamine mixture is useful.

Amine also can be heterocyclic polyamines, and they are ethylenimine, azetidine, Azolidines, four-and dihydropyridine, pyrroles, indoles, piperidines, imidazoles, two-and imidazolidine, piperazine, isoindole, purine, morpholine, thiomorpholine, N-aminoalkyl group morpholine, N-aminoalkyl group thiomorpholine, N-aminoalkyl piperazine, N, N ¹-Diaminoalkyl piperazine, azepines, azocine, azonine, Azecine, two or more mixtures of the dihydro of above-mentioned each compound and tetrahydrochysene derivative and these heterocyclic amines.Preferred heterocyclic amine is saturated 5 yuan and 6 yuan of heterocyclic amines, particularly piperidines that only contain nitrogen, oxygen and/or a sulphur on heterocycle, piperazine, thiomorpholine, morpholine, tetramethyleneimine etc.Piperidines, the piperidines that aminoalkyl replaces, piperazine, the piperazine morpholine that aminoalkyl replaces, the morpholine that aminoalkyl replaces, tetramethyleneimine and the amino pyridine alkane that replaces are particularly preferred.Usually the aminoalkyl substituent is to be substituted on the nitrogen-atoms that forms a heterocyclic part.The specific examples of heterocyclic amine comprises N-ammonia propane morpholine, N-aminoethyl piperazine and N, N ¹-diamino ethyl piperazine.

The polyamine mixture of other useful types is residues that above-mentioned polyamine mixture is left after extracting, and is referred to as " polyamine substrate ".Generally, can it have and be less than 2% at the bottom of the alkylidene group polyamine, often to be less than 1%(weight) material in about boiling below 200 ℃.The typical sample of this alkylidene group polyamine derive from " Dow Chemical Company, Freeport, Texas; be labeled as " E-100 "; its proportion (15.6 ℃) is 1.0168, nitrogenous 33.15%(weight), viscosity (40 ℃) is 121 Cts(li ponds).The gas chromatographic analysis of this sample contains about 0.93% " gently holding the gold-plating branch " (possible major part is DETA), 0.72%TETA, and 21.74% tetren and 76.61% or higher penten, by weight.These alkylidene group polyamine substrates comprise ring-type product and the diethylenetriamine as piperazine and so on, more senior analogue such as Triethylenetetramine (TETA).

These alkylidene group polyamine substrates can be separately and acylation reaction, and amino reactant in the case mainly is made up of alkylidene group polyamine substrate, perhaps they can with other amine, polyamine or their mixture one work.

Another useful polyamine is the condensation reaction between at least a oxy-compound and at least a polyamine reactant that contains at least one primary amine groups or secondary amine.Oxy-compound is polyhydric alcohol and many azanols preferably.Polyhydric alcohol contains 2 to about 10, preferred 2 to about 6, and particularly 2 to about 4 hydroxyls to 40 aliphatic carbon atom, and preferred 2 to about 30, and particularly 2 to about 10 carbon atoms.Polyhydric alcohol comprises ethylidene glycol (two-, three-four ethylidene glycols), trimethylene glycol (comprise two-, three-four trimethylene glycols, glycerol, butyleneglycol, hexylene glycol, sorbyl alcohol, arabitol, mannitol, sucrose, fructose, glucose, cyclohexane diol, tetrahydroxybutane and tetramethylolmethane (comprise two-and tripentaerythritol).Preferred oxy-compound is many azanols.Many azanols comprise above-mentioned any monoamine and to contain 2-about 20, the reaction of the alkylene oxide (as oxyethane, propylene oxide, butylene oxide ring etc.) of preferred about 4 carbon atoms of 2-.The example of polyamine compounds comprises tripropanolamine, three (methylol) aminomethane, 2-amino-2-methyl-1,3-propane diol, N, N, N ¹, N ¹-four (2-hydroxypropyl) quadrol and N, N, N ¹, N ¹-four (2-hydroxyethyl) quadrol.Preferred three (methylol) ammonia methane (THMA).

The polyamine reactant that forms condensed products or amine condensation with the reaction of polyhydric alcohol or amine as mentioned above.Preferred polyamine reactant comprises Triethylenetetramine (TETA) (TETA), tetren (TEPA), penten (PEHA) and as the polyamine mixture of above-mentioned " amine substrate ".

The condensation reaction of polyamine reactant and oxy-compound preferably at high temperature normally about 60 ℃-Yue 265 ℃, preferred about 220 ℃-Yue 250 ℃, is carried out in the presence of acid catalyst.

Amine condensation product and preparation method thereof is described in PCT bulletin WO86/05501, and its condensation product and preparation method thereof is for reference at this.Preparation method's illustration of this class polyamine condenses is in following example M-1.

Illustration is in following example M-1.

Example M-1

With 1299g HPA Taft amine (the supply of commodities amine substrate of Union Carbide Co., generally contain 34.1%(weight) nitrogen, primary amine nitrogen is distributed as 12.3%(weight), secondary amine nitrogen is distributed as 14.4%(weight), tertiary amine nitrogen is distributed as 7.4%(weight)) and the mixture heating up to 60 of three (methylol) aminomethane (THAM) aqueous solution of 727g40% ℃, add the 85%H of 23g again ₃PO ₄Then mixture was heated to 120 ℃ in 0.6 hour.Under nitrogen purging, mixture was heated to 150 ℃ in 1.25 hours,, kept 5 hours at 230-235 ℃ then, be heated to 240 ℃ and kept 5 hours again in 0.75 hour at 240-245 ℃ then in being heated to 235 ℃ more than 1 hour.Mixture is cooled to 150 ℃, filters, obtain the required product of 1221g with super-cell.

Metal deactivator also can be triazole and at least a nitrogen compound (above-mentioned carboxyl dispersion agent) that is selected from acidylate, and alkyl replaces the reaction product of amine (following amine dispersion agent) and this (Mannich) reaction product of Manny (this dispersion agent of following Manny).

The nitrogen compound of acidylate comprises the reaction product of amine and carboxylic acylating agent (being the acylating agent in " carboxylic acid (A) (I) (a) " as above-mentioned title).Useful amine is the amine that above-mentioned and benzotriazole reaction form metal deactivator, generally is polyamines, preferred ethamine, amine substrate or amine condenses.

Can replace amine with the hydrocarbon of triazole reaction is well known to those skilled in the art.They are in USPatents 3,275,554; 3,438,757; 3,454,555; 3,565,804; Disclosed in 3,755,433 and 3,822,289.These patents replace the reference of amine and preparation method thereof at this as hydrocarbon.

Generally, hydrocarbon replaces amine with alkene and olefin polymer (polyolefine) and amine (monoamine or polyamines) prepared in reaction.Polyolefine can be any polyolefine under above-mentioned " carboxylic acid (A) (I) (a) " title.Amine can be any amine that forms metal deactivator with the benzotriazole reaction.These examples that replace amine comprise poly-(propylene) amine, N, and N-dimethyl-N-gathers (ethylene/propene) amine (monomer mole ratio is 50: 50), polybutene amine, N, N-two (hydroxyethyl)-N-polybutene amine, N-(2-hydroxypropyl)-N-polybutene amine, N-polybutene amine, N-polybutene morpholine, N-gathers (butylene) quadrol, and N-gathers (propylene) trimethylene diamines, N-gathers (butylene) diethylenetriamine, N ¹, N ¹-poly-(butylene) tetren, N, N-dimethyl-N ¹-poly-(propylene)-1,3-propylene diamine etc.

Triazole also can with this reaction of Manny.This reaction product of Manny is to use at least a aldehyde, and at least a above-mentioned amine and at least a hydroxy aromatic compound react formation as phenol.Reaction can be in room temperature to about 225 ℃, usually at about 50 ℃ to about 200 ℃, preferably carry out under about 75 ℃ to about 125 ℃, and the mol ratio of hydroxy aromatic compound/formaldehyde/amine is about 1: 1: 1 to about 1: 3: 3.This reaction product of useful Manny is described in the following patent: USP3,980,569; USP3,877,899; USP 4,454, and 059.These patents at this as the reference of (also claiming Manny this dispersion agent) of this reaction product of Manny.

Aminotriazole, triazole acylated amine, triazole-hydrocarbon replace the preparation of amine and this reaction product of triazole Manny and can will react after the reagent mix.Temperature of reaction is about 15 ℃ to 160 ℃, preferred about 60 ℃ to about 140 ℃.Triazole-amine, triazole acylated nitrogen compound, triazole-hydrocarbon replaces amine and this reaction product of triazole-Manny can any ratio be reacted, preferred equivalent ratio.

Phosphorous anti-wear agent

In one embodiment, the high-alkali product of sulfuration of the present invention is used in combination with at least a phosphorous anti-wear agent.In this specific embodiments, the amount of phosphorous anti-wear agent in lubricant of the present invention and sense liquid is enough to give lubricant and sense liquid with abrasion resistance.In general, its amount can reach about 20%(weight of lubricant or sense total amount of liquid), preferably about 10%(weight).Be typically about 0.01% about 0.05% or about 0.08%(weight) to about 2% 1% or 0.5%(weight).

Operable phosphorous anti-wear agent comprises phosphorous acid, phosphorous acid ester, phosphite or their derivative.Phosphoric acid comprises phosphoric acid, phosphonic acids, phosphonous acid and thiophosphoric acid (comprising phosphorodithioic acid and monothio phosphoric acid, thiophosphorous acid and phosphonothionic acid).

In one embodiment, phosphorous anti-wear agent is a Monophosphate, it be with phosphorus acid or anhydride and contain 1 or about 3 carbon atoms to about 30 or about 24 or the pure prepared in reaction of about 12 carbon atoms.The phosphorus acid or anhydride generally is inorganic phosphorus reagent such as Vanadium Pentoxide in FLAKES, phosphorus trioxide, phosphorus tetroxide, phosphoric acid, Phosphorates phosphorus Halides or rudimentary phosphoric acid ester etc.Each ester group of rudimentary phosphoric acid ester contains 1 to about 7 carbon atoms.Phosphoric acid ester can be one, two or triguaiacyl phosphate.

The alcohol that is used to prepare phosphoric acid ester comprises butanols, amylalcohol, hexanol, octanol, oleyl alcohol and cresols., reoxidize the senior synthetic single hydroxy alcohol that forms with hydrolysis and also share through the polymerization of organoaluminum catalytic oligomerization by oxo synthesis (for example 2-ethylhexyl), Aldol condensation or alpha-olefin (particularly ethene).Some preferred single hydroxy alcohols and alcohol mixture comprise commercially available " Alfol " (Continental Oil Corporation).Alfol 810 is that to contain mainly be straight chain and alcohol mixture 8-10 carbon atom.Alfol 12 contains most of C ₁₂The alcohol mixture of Fatty Alcohol(C12-C14 and C12-C18).Alfol 1218 is to be the mixture that contains the synthetic one-level straight chain alcohol of 12-18 carbon atom mainly.Alfol+ alcohol is C ₁₈-C ₂₈The mixture of primary alcohol, major part are C ₂₀Alcohol (activity coefficients and relative volatilities).Alfol 22+ alcohol is C ₁₈-C ₂₈Primary alcohol mainly contains C ₂₂Alcohol.These Alfol alcohol can contain suitable percentage ratio (reaching 40%(weight)) the paraffinic hydrocarbon compound, can before reaction, be removed when needing.

The example of another commercially available alcohol mixture is Adol 60, and it comprises about 75%(weight) straight chain C ₂₂Primary alcohol, about 15%(weight) C ₂₀Primary alcohol and about 8% C ₁₈And C ₂₄Alcohol.Adol 320 mainly comprises oleyl alcohol, and Adol alcohol is sold by Ashland Chemical.

Procter ﹠amp; It is C that Gamble Co. provides a series of chain lengths ₈To C ₁₈Natural triglycerides single hydroxyl fatty alcohol mixture of deriving and obtaining.It mainly is 12,14 that these mixtures contain, the Fatty Alcohol(C12-C14 and C12-C18) of the difference amount of 16 or 18 carbon atoms.For example CO-1214 contains 0.5%C ₁₀Alcohol, 66.0%C ₁₂Alcohol, 26.0%C ₁₄Pure and mild 6.5%C ₁₆The mixture of alcohol.

Another group commercial mixture comprises " Neodol " product that Shell Chemical Co. provides.For example Neodol 23 is C ₁₂And C ₁₃The mixture of alcohol; Neodol 25 is C ₁₂And C ₁₃The mixture of alcohol; Neodol 45 is C ₁₄To C ₁₅The linear alcohol mixture, Neodol 91 is C ₆, C ₁₀, C ₁₁The mixture of alcohol.

The aliphatics glycol also is fit to, and they comprise that the trade mark that Ashland Oil company provides is Adol 114 and Adol 158 products, and the former is derived from straight chain C ₁₁-C ₁₄Alpha-olefin, the latter is derived from C ₁₅-C ₁₈Alpha-olefin.

The example of useful phosphoric acid ester comprises the phosphoric acid ester that is formed by phosphorus acid or anhydride and cresols reaction.

In one embodiment, phosphoric acid ester is the monothio phosphoric acid ester.The monothio phosphoric acid ester is made by a sulphur source and phosphorous acid dialkyl.The sulphur source can be the one or more sulphur compounds in elementary sulfur or above-mentioned " sulphur or sulphur source (B) " title.The sulphur source can be the alkene of single sulphur compound such as sulphur coupling or the phosphorodithioate of sulphur coupling.Elementary sulfur is preferred sulphur source.The preparation of monothio phosphoric acid ester is disclosed in USP4, and 755,311 and PCT bulletin WO87/07638, in this reference as the preparation of the sulphur source of monothio phosphoric acid ester, preparation monothio phosphoric acid ester and monothio phosphoric acid ester.

The monothio phosphoric acid ester can form in lubricant, adds the phosphorous acid dialkyl in the lubricating composition in sulfur-bearing source.Phosphorous acid ester can (promptly about 30 ℃ extremely about 100 ℃ or higher) form the monothio phosphoric acid ester with the reaction of sulphur source under mixing condition.Also find under the condition of lubricating composition in the engine of work to form the monothio phosphoric acid ester.

In one embodiment, the phosphorated anti-wear agent is a phosphorodithioic acid.Phosphorodithioic acid can form intermediate with epoxide or glycol reaction, and intermediate reacts with phosphoric acid, acid anhydride or lower member ester again.Epoxide is aliphatic epoxide or Styrene oxide 98min. normally.The example of useful epoxide comprises oxyethane, propylene oxide, butylene oxide ring, octylene oxide, epoxy dodecane, Styrene oxide 98min. etc.Preferred propylene oxide.Glycol can be to contain about 12 of 1-, about 6 of preferably about 2-, the particularly aliphatic diol or the aromatic diol of 2 or 3 carbon atoms.Aliphatic diol comprises ethylene glycol, propylene glycol, triglycol etc.Aromatic diol comprises quinhydrones, catechol, Resorcinol etc.They are described in USP3, in 197,405, at this as phosphorodithioic acid, glycol, epoxide, the reference of inorganic phosphorus reagent and its reaction method.

The preparation of the phosphoric acid ester that following example P-1 and P-2 explanation are useful

Example P-1

64g lasted in 58 ℃ added two (4-methyl-2-amyl group) phosphorodithioic acid hydroxypropyl acrylates of 514g (two (4-methyl-2-amyl group) phosphorodithioic acid makes with 1.3 moles of propylene oxide reactions in 25 ℃) in 45 minutes.Mixture mixes with super-cell 75 ℃ of heating 2.5 hours, filters down in 70 ℃.The phosphorus content of filtrate is a 11.8%(weight), sulphur content 15.2%(weight), acid number is a 87(bromjophenol blue indicator).

Example P-2

With 667g Vanadium Pentoxide in FLAKES and 3514﹠amp; Diisopropyl disulfide heated 3 hours at 85 ℃ in the 50 ℃ times mixtures with the reaction product of 986g propylene oxide for phosphoric acid, filtered.Filtrate phosphorus content 15.3%(weight), sulphur content 19.6%(weight), acid number 126(bromjophenol blue indicator).

When phosphoric acid ester is acidity, can form corresponding amine or metal-salt with amine compound or metal base reaction.The salt of these phosphoric acid ester can prepare respectively, adds lubricating composition then; Also can when mixing the formation lubricating composition with other components, phosphoric acid ester form salt.Phosphoric acid ester can also form salt with the alkaline matter that can react in the lubricating composition such as basic nitrogen compound (for example carboxylic dispersants) and high alkalinity material.

The amine salt of phosphoric acid ester can be prepared by ammonia or one-level, secondary or tertiary amine or their mixture.Primary amine title in the above is narration in " metal deactivator ".

Secondary amine comprises dialkylamine, there are two at the alkyl described in the primary amine, comprise so commercially available aliphatics secondary amine, as above-mentioned Armeen amine and mixing dialkylamine, for example an alkyl is an aliphatic amide, another alkyl is the low alkyl group of 1-7 carbon atom, as methyl, ethyl, n-propyl, sec.-propyl, butyl etc., perhaps another alkyl has other alkyl non-reacted or polar substituent (CN, alkyl, carboxyl, acid amides, ether, thioether, halogen, sulfoxide, sulfone), can not destroy the basic hydrocarbon character of group.

Other useful primary amines are one-level ether amine R " OR ' NH ₂, wherein R ' is the alkylidene group that contains about 6 carbon atoms of about 2-, R " is the alkyl of about 150 carbon atoms of about 5-.These one-level ether amine generally are with pure R, and " OH and unsaturated nitrile preparation, " base can be with containing the alkyl that reaches 150 carbon atoms approximately for the R of alcohol.In general, also be because efficient and concern that economically alcohol is linear or branched fatty alcohol, R " carbon atom reach about 50, preferably reach about 26, most preferably from about 6-is about 20.Nitrile carbon reactant atomicity can be from about 6 of about 2-, preferred vinyl cyanide.Ether amine is known commercially available prod, by Nars Chemical Co, and Atlanta, Georgia produces and provides, merchant's name SUPFARM

Typical ether amine molecule amount is about 150-about 400.Preferred ether amine is SURFAM P14B(oxygen in last of the ten Heavenly stems propylamine), the linear C of SURFAM P16A( ₁₆), SURFAM P17B(oxygen propylamine in three last of the ten Heavenly stems).Above-mentioned carbon chain lengths (is C ₁₄Deng) and literary composition back used be approximation, and comprise oxygen-ether linkage.For example, C ₁₄SURFAM has following molecular formula: C ₁₀H ₂₁OC ₃H ₆NH ₂

The amine that is used to prepare amine salt can be azanol.In one embodiment, these azanols can be represented by following formula:

R in the formula ¹Be alkyl, generally contain about 30 carbon atoms of about 6-; R ²Be ethene or propenyl; R ³Be to contain the alkylidene group that reaches 5 carbon atoms; A is 0 or 1; Each R ⁴Be hydrogen or low alkyl group; Each is that 0-is about 10 independently for X, Y and Z, and condition is that one of X, Y and Z are 1 at least at least.

These azanols can be with technology well known in the art preparation, and many have a supply of commodities.For example, contain at least about the primary amine of 6 carbon atoms can with the alkylene oxide reaction of different amounts, as ethylene oxide, third alkylene oxide etc.Primary amine comprises amine mixt, as derive from fatty oil (for example tallow oil, Sperm whale oil, coconut wet goods) hydrolysis, the aliphatic amide specific examples that contains about 30 carbon atoms of about 6-comprises saturated and unsaturated fatty acids amine such as octylame, decyl amine, lauryl amine, stearylamine, oleyl amine, Semen Myristicae amine, palmitamide, n-Laurylamine and octadecane amine.

A is that 0 useful azanol comprises 2-hydroxyethyl hexylamine in the following formula, 2-hydroxyethyl octylame, 2-hydroxyethyl pentadecyl amine, 2-hydroxyethyl oleyl amine, 2-hydroxyethyl soybean amine, two (2-hydroxyethyl) hexylamine, two (2-hydroxyethyl) oleyl amine and its mixture, at least one is at least 2 also to comprise in the following formula of similar quantity X and Y, for example 2-hydroxy ethoxy hexylamine.

A is that 0 azanol is by Armak Chemical Division of Akzona in many following formulas, Inc., and Chicago, Illinois provides, its merchant " Ethomeen " and " Propomeen " by name.The specific examples of these products comprises Ethomeen C/15, is the ethylene oxy condenses that contains the coconut fatty acid of about 5 molar ethylene oxygen; Ethomeen C/20 and C/25 are for containing about 10 and the ethylene oxy condensation product of the coconut fatty acid of 15 molar ethylene oxygen respectively; Ethomeen O/12 contains the ethylene oxy condensation product of the oleyl amine of about 2 molar ethylene oxygen for every mole of amine; Ethomeen S/15 and S/20 contain the stearylamine ethylene oxy condensed products of about 5 and 10 molar ethylene oxygen respectively for every mole of amine; Ethomeen T/12, T/15 and T/25 contain the ethylene oxy condensed products of the tallow amine of about 2,5 and 15 molar ethylene oxygen respectively for every mole of amine; Propomeen O/12 is the condensed products of one mole of oleyl amine and 2 mol propylene oxygen.

A is that the example of 1 commodity alkoxylated amines comprises Ethodumeen T/13 and T/20 in the following formula; The ethylene oxy condensed products that contains the N-tallow trimethylene diamines of 3 and 10 molar ethylene oxygen for every mole of diamines respectively.

Aliphatic polyamine, diamines comprise an alkyl or dialkyl group, symmetrical or asymmetric quadrol, propylene diamine (1,2 or 1,3) and above-mentioned polyamine analogue.The commodity fat polyamine that is fit to is a Duomeen C(N-cocoa-1, the 3-diaminopropanes; Duomeen S(N-soybean-1, the 3-diaminopropanes); Duomeen T(N-tallow-1, the 3-diaminopropanes) and Duomeen O(N-oil base 1, the 3-diaminopropanes)." Duomeen " is Armak Chemical Co., Chicago, the commodity diamines described in the Product Data Bulletin No.7-10R1 of Illinois.In one embodiment, secondary amine can be a cyclammonium, as piperidines, piperazine, morpholine etc.

The phosphoric acid ester metal-salt is with metal base and phosphoric acid ester prepared in reaction.Metal base can be with any form easily, as oxide compound, oxyhydroxide, carbonate, vitriol, borate etc.Metal in the metal base comprises I A, II A, I B family to VII B and VIII family metal (the CAS version periodic table of elements), and they are basic metal, alkaline-earth metal and transition metal.In one embodiment, the available metal is an II A family metal, as calcium and magnesium; II B family metal, as zinc, or VII B family's metal such as manganese, preferably magnesium, calcium, manganese or zinc, more preferably magnesium, calcium, zinc, particularly magnesium and zinc.The specific examples of useful metal base comprises the alkali in the above-mentioned title " metal base (A) (III) ".

Following example P-3 to P-6 has illustrated the preparation of useful phosphate ester salt.

Example P-3

Adding molecular-weight average down in 25-60 ℃ in the filtrate of 217g example P-1 is 191 commodity fat primary amine 66g, and fat group wherein is the mixture that contains uncle's aralkyl group of 11-14 carbon atom.The phosphorous 10.2%(weight of resulting product), nitrogenous 1.5%(weight), acid number is 26.3.

Example P-4

The filtrate of 1752g example P-2 is mixed with the aliphatics primary amine that 764g is used for example P-3 down in 25-82 ℃.The phosphorous 9.95%(weight of the product of gained), nitrogenous 2.72%(weight), sulfur-bearing 12.6%(weight).

Example P-5

(a) the 852g Vanadium Pentoxide in FLAKES is added in the 2340g isooctyl alcohol, last 3 hours.Temperature is risen by room temperature, but keeps below 65 ℃.With mixture heating up to 90 ℃, and remained on this temperature 3 hours after adding.Add 30g silicon and help filtrate, filtering mixt.The phosphorous 12.4%(weight of filtrate), bromjophenol blue acid neutralization value is 192, and phenolphthalein acid neutralization value is 290.

(b) filtrate that will derive from (a) is mixed with 200g toluene, 130g Dormant oils, 1g acetate, 10g water and 45g zinc oxide, is heated to 60-70 ℃ under the pressure of 30 holders.Filter the product mixture that obtains with the silicon flocculating aids.Filtrate contains zinc 8.58%(weight), phosphorous 7.03%(weight).

Example P-6

The 208g Vanadium Pentoxide in FLAKES is added by 280g third alkylene oxide and 1184gO, and O '-diisobutyl phosphorodithioic acid is in the 30-60 ℃ of available product of reaction.Interpolation is to carry out under 50-60 ℃ temperature, with the mixture heating up to 80 that obtains ℃, remains on this temperature 2 hours then.Temperature is remained on 30-60 ℃, add the commercially available aliphatics primary amine of 384g example 3.Mixture is filtered the phosphorous 9.31%(weight of filtrate), sulfur-bearing 11.37%(weight), nitrogenous 2.50%(weight) and, base number 6.9(bromjophenol blue indicator).

Phosphorous anti-wear agent also can be a phosphorous acid ester, in one embodiment, phosphorous acid ester is two-or the trialkyl phosphorous acid ester.The carbonatoms of each alkyl is preferably from 1 to about 24, preferred 1 to about 18, and more preferably from about 2 to about 8.Each alkyl can be independently alkyl, alkenyl or aryl.When alkyl was aryl, it contained at least about 6 carbon atoms, and preferably about 6 to about 18 carbon atoms.Alkyl and non-limiting examples of alkenyls comprise propyl group, butyl, hexyl, heptyl, octyl group, oil base, inferior oil base, stearyl etc.The example of aryl comprises phenyl, naphthyl, and heptyl phenol is quick.Preferably each alkyl is propyl group independently, butyl, amyl group, hexyl, heptyl, oil base or phenyl, preferred butyl, oil base or phenyl, particularly butyl or oil base.Phosphorous acid ester and preparation method thereof is known, and is many existing commercially available.Useful especially phosphorous acid ester is phosphorous acid dibutyl ester, tricresyl phosphite oil base ester, triphenyl phosphite.

In one embodiment, phosphorous anti-wear agent can be the phosphorated acid amides.The phosphorated acid amides can be by above-mentioned phosphoric acid, preferably phosphorodithioic acid and unsaturated amides reaction and producing.The example of unsaturated amides comprises acryloyl, N, N-methylene bisacrylamide, Methacrylamide, crotonamide etc.The reaction product of phosphoric acid and unsaturated amine can form coupling compound with coupling compound (as formaldehyde or Paraformaldehyde 96) reaction again.The phosphorated acid amides is known in the art, and at USP4, and is open in 876,374 and USP4,770,807, at this as the reference that contains phosphamidon and preparation method thereof.

Following example P-7 and the useful preparation method who contains phosphamide of P-8 explanation.

Example 7

In nitrogen atmosphere with 1017gO, O ¹-two (4-methyl-2-amyl group) phosphorodithioic acid is added in the 213g acrylamide.Exothermic heat of reaction to 65 ℃, and kept 1-3 hour at 65-75 ℃.Product mixture passes through diatomite filtration.Filtrate is required product, phosphorous 7.65%(weight), nitrogenous 3.51%(weight), sulfur-bearing 16.05%(weight).

Example P-8

In nitrogen atmosphere with the 50%(weight of 537g) acrylamide solution adds 1494gO, O ¹The mixture of-diisooctyl phosphorodithioic acid and 800g toluene lasts 1 hour.The reaction mixture heat release is to about 53 ℃.Add 64 parts of polyoxymethylene and 18g tosic acid hydrate.With mixture backflow (91-126 ℃) heating 4 hours, collect 305g water simultaneously.With mixture be cooled to 90 ℃ and add the 50%(weight of 7.6g) aqueous sodium hydroxide solution, continue to be cooled to about 30 ℃ and impose vacuum (15mmHg).When temperature rises to 110 ℃, steam toluene.Go out residue with diatomite filtration, filtrate is required product, phosphorous 6.90%(weight), nitrogenous 2.92%(weight).

In one embodiment, phosphorous anti-wear agent is the phosphorated carboxylicesters.They can react with above-mentioned phosphoric acid (as phosphorodithioic acid) and a undersaturated carboxylic acid or ester (as vinyl acids or diallylacetic acid or ester) and prepare.If the use carboxylic acid can react the formation ester with itself and alcohol.

The vinyl acetate of carboxylic acid can be by RCH=CHO(O) CR ' representative, wherein R is hydrogen or the alkyl that contains about 30 carbon atoms of 1-, preferred hydrogen or contain the alkyl of about 12 carbon atoms of 1-, more preferably hydrogen; R ' is the alkyl that contains about 30 carbon atoms of 1-, the preferred about twelve carbon atom of 1-, more preferably about 8 carbon atoms of 1-.The example of vinyl ester comprises that vinyl acetate is waken up, 2 ethyl hexanoic acid vinyl acetate, vinyl butyrate and Vinyl crotonate.

In one embodiment, esters of unsaturated carboxylic acids is the ester of a unsaturated carboxylic acid, as fumaric acid, and toxilic acid, vinylformic acid, methacrylic acid, methylene-succinic acid, citraconic acid etc.Esters of unsaturated carboxylic acids can formula RO-(O) CHC=CH-C(O) the OR representative, wherein R is the alkyl that independently contains about 18 carbon atoms of 1-, preferably 1-is about 12, particularly about 8 carbon atoms of 1-.

The example of useful in the present invention esters of unsaturated carboxylic acids comprises methacrylic ester, the ethyl propylene acid esters, the 2-ethylhexyl acrylate, the 2-hydroxyethylmethacry,ate, ethyl-methyl acrylate, 2-hydroxyl-metacrylate, the 2-hydroxy propyl methacrylate, 2-hydroxypropyl acrylate, ethyl maleic acid ester, butyl maleic acid ester and 2-ethylhexyl maleic acid ester.Above-mentioned example also comprises toxilic acid, the monoesters of fumaric acid and citraconic acid and diester.

In one embodiment, phosphorous anti-wear agent is the reaction product of phosphoric acid and vinyl ether.Vinyl ether is with formula R-CH ₂=CH-OR ' representative, wherein R is hydrogen or contains about 30 carbon atoms of 1-, preferred 1-is about 24, more preferably the alkyl of the about twelve carbon atom of 1-; R ' is that to contain 1-about 30, and preferred 1-is about 24, more preferably the alkyl of the about twelve carbon atom of 1-.The example of vinyl ether comprises methoxy ethylene, vinyl propyl ether, vinyl 2-ethyl hexyl ether etc.

Sanitising agent and dispersion agent:

Lubricating composition of the present invention and sense liquid can contain one or more sanitising agent that ash or Ashless type are arranged or dispersion agents.It is the oil soluble neutrality or the basic salt of alkali or alkaline-earth metal and sulfonic acid, carboxylic acid or organic phosphoric acid that the example of sanitising agent of grey type is arranged, organic phosphoric acid is a feature with at least one direct C, as handle the C that makes by olefin polymer (for example molecular weight is 1000 polyisobutene) usefulness-phosphorization agent, phosphorization agent such as phosphorus trichloride, phosphorus heptasulfide, thiophosphoric anhydride, phosphorus trichloride ten sulphur, white phosphorus ten halogenation sulphur or thiophosphoryl chlorides.The most frequently used salt of this type of acid is sodium, potassium, lithium, calcium, magnesium, strontium, the salt of barium.These have grey sanitising agent to be described in more detail in the used high alkalinity product (A) of above preparation sulfuration high alkalinity product.

Ashless sanitising agent and dispersion agent each when burning do not produce as the non-volatile substance of boron oxide or Vanadium Pentoxide in FLAKES and so on because of it is formed in, but containing metal not usually, thereby when burning, do not produce metallic ash content.The ashless sanitising agent of many types is known in the art, all is applicable to lubricating composition of the present invention.Be described below:

(1) contain at least about 34, preferably the carboxylic acid of at least 54 carbon atoms (or derivatives thereof) with as the nitrogenous compound of ammonia and so on, as the organic hydroxy compounds of phenol and alcohols and/or the reaction product of alkaline inorganic material.The example of these carboxylic dispersants is described in BP 1,306,529 and following United States Patent (USP) in:

3,163,603??3,351,552??3,541,012

3,184,474??3,381,022??3,543,678

3,215,707??3,399,141??3,542,680

3,219,666??3,415,750??3,567,637

3,271,310??3,433,744??3,574,101

3,272,746??3,444,170??3,576,743

3,281,357??3,448,048??3,630,904

3,306,908??3,448,049??3,632,510

3,311,558??3,451,933??3,632,511

3,316,177??3,454,607??3,697,428

3,340,281??3,467,668??3,725,441

3,341,542??3,501,405??4,234,435

3,346,493??3,522,179??4,938,881

Re26,433

(2) relatively high-molecular weight aliphatic series or alicyclic ring halogenide and amine, the reaction product of oxyalkylene polyamines preferably.These can be described as " amine dispersion agent ", and the example is found in following United States Patent (USP):

3,275,554??3,454,555

3,438,757??3,565,804

(3) alkyl contains the reaction product of alkylphenol and the aldehyde (particularly formaldehyde) and the amine (particularly oxyalkylene polyamines) of about 30 carbon atoms at least, can be described as " this dispersion agent of Manny ".These dispersion agents are described in the following United States Patent (USP):

2,459,112??3,442,808??3,591,598

2,962,442??3,448,047??3,600,372

2,984,550??3,454,497??3,634,515

3,036,003??3,459,661??3,649,229

3,166,516??3,461,172??3,697,574

3,236,770??3,493,520??3,725,277

3,355,270??3,539,633??3,725,480

3,368,972??3,558,743??3,726,882

3,413,347??3,586,629??3,980,569

(4) with urea, thiocarbamide, dithiocarbonic anhydride, aldehyde, ketone, carboxylic acid, hydrocarbon substituted succinyl oxide, nitrile, epoxide, boron compound, phosphorus compound etc. amine or this dispersion agent of Manny are carried out the product that aftertreatment obtains.The example of this class product is described in following United States Patent (USP):

3,036,003??3,282,955??3,493,520??3,639,242

3,087,936??3,312,619??3,502,677??3,649,229

3,200,107??3,366,569??3,513,093??3,649,659

3,216,936??3,367,943??3,533,945??3,658,836

3,254,025??3,373,111??3,539,633??3,697,574

3,256,185??3,403,102??3,573,010??3,702,757

3,278,550??3,442,808??3,579,450??3,703,536

3,280,234??3,455,831??3,591,598??3,704,308

3,281,428??3,455,832??3,600,372??3,708,422

(5) as decyl-octyl methacrylate, the multipolymer of the molten monomer of vinyl decyl ethers and high molecular weight olefin oil and the monomer that contains polar substituent (for example aminoalkyl acrylate or acrylamide and polyoxyethylene replace acrylate).They are called " polymeric dispersant ".The example is disclosed in following United States Patent (USP):

3，329，658??3，666，730

3，449，250??3，687，849

3，519，565??3，702，300

These patents are in this reference as ashless dispersant.

Auxiliary extreme pressure and/or wear-resistant, suppress corrosion and inhibited oxidation agent

Lubricating composition of the present invention and sense liquid can contain one or more anti-extreme pressures and/or anti-wear agent, corrosion inhibitor and/or oxidation retarder.Can be included in the auxiliary anti-extreme pressure agent and the corrosion inhibitor of lubricant of the present invention and sense liquid, the example of oxidation retarder has chlorinated aliphatic (as clorafin), organic sulfide and polysulfide are (as phenyl disulfide, two sulphur dichlorobenzenes, four sulphur dibutyl, the sulfuration Witconol 2301, sulphurized alkyl phenols, sulfuration limonene and sulfuration terpenes), phosphosulfurized hydrocarbon (as phosphoric sulfide and turps or Witconol 2301 reaction product), phosphide comprises that mainly phosphorous acid two hydrocarbon and trialkyl are (as dibutyl phosphite, phosphorous acid two heptyl esters, phosphorous acid two cyclohexyls, phosphorous acid amyl group phenyl ester, phosphorous acid diamyl phenyl ester, tridecyl phosphite, phosphorous acid distearyl ester, phosphorous acid dimethyl esters naphthalene ester, phosphorous acid oil base ester 4-amyl group phenylester, the phenylester that phosphorous acid polypropylene (MW500) replaces, the phosphorous acid phenylester that diisobutyl replaces), the thiocarbamate metal-salt is (as the dioctyl zinc dithiocarbamate, heptyl phenyl dithiocarbamic acid barium), dithiocarbamic acid and vinylformic acid, methacrylic acid, toxilic acid, the dithiocarbamate that the reaction product of fumaric acid or itaconicacid ester obtains, the dithiocarbamate that contains the acid amides of producing by dithiocarbamic acid and acrylamide, the dithiocarbamate of alkene coupling, the dithiocarbamate of sulphur coupling.The dithiophosphates of II family metal such as dicyclohexyl zinc dithiophosphate, the dioctyl zinc dithiophosphate, two (heptyl phenyl) phosphorodithioic acid barium, the zinc salt of dinonyl phosphorodithioic acid calcium and the phosphorodithioic acid that obtains by thiophosphoric anhydride and one mole of Virahol and n-hexyl alcohol mixture reaction.

Above-mentioned many auxiliary extreme pressure agent and corrosion-oxidation retarder also can be used as anti-wear agent.Zinc dialkyl dithiophosphate is the example of knowing.

Other additives:

Lubricating composition of the present invention and sense liquid can contain one or more pour point reducers, colouring stabilizer and/or kilfoam.Pour point reducer is the additive of the particularly useful type that often contains in described lubricating oil.In oil-based composition, be that this area is known and known to improve low-temperature performance with such pour point reducer.For example, C.V.Smalheer and R.Kennedy Smith, the 8th page of " Lubricant Additives " (Lezius-Hiles Co.Publishers, Cleveland, Ohio, 1967th) are described.Now be provided in this for its relevant open reference.

The enforcement of useful pour point reducer is polymethacrylate, polyacrylic ester, polyacrylamide, the condensation product of halo paraffinic hydrocarbon and aromatic compound, vinyl carboxylates, the tripolymer of dialkyl group fumarate, the vinyl alcohol that lipid acid and alkyl vinyl ether generate.Be used for the object of the invention pour point reducer, its technology of preparing and purposes and be described in United States Patent (USP) 2,387,501; 2,015,748; 2,655,479; 1,815,022; 2,191,498; 2,666,746; 2,721,877; In 2,721,878 and 3,250,715, provide the ginseng ginseng at this.

Kilfoam is used for reducing or preventing the formation of stable foam.Typical case's kilfoam comprises silane or organic polymer.Other anti-foaming composition is narrated in the 125-162 page or leaf of " Foam Control Agents " (Noyes Data Corp., 1976) at Henry T.Kerner.

Lubricating grease:

Lubricating composition of the present invention can be a lubricating grease, and wherein above-mentioned anyly have the oil of lubricant viscosity all to can be used as vehicle.Lubricant generally adopts the amount of lubricating oil to be enough to the total grease composition of balance during with the form of lubricating grease, and damp oil/fat composition will contain the thickening materials of different amounts and other binder component so that needed character to be provided.Generally, grease contains about 0.01-about 20% or 30%(weight) the present invention vulcanize the high alkalinity product.

Many thickening materials all can be in preparation of greases of the present invention.Thickening material comprises the alkali or the alkaling earth metal base of lipid acid and about 30 carbon atoms of about 12-.Used metal typical be sodium, lithium, calcium and barium.The example of fatty substance comprises stearic acid, oxystearic acid, Vinlub, oleic acid, palmitinic acid, tetradecanoic acid, oleic acid and hydrogenated fish oil.

Other thickening material comprises salt and salt-soap mixture, as stearic acid-calcium acetate (USP2,197,263), stearic acid-barium acetate (USP2,564,561), stearic acid-sad-calcium acetate mixture (USP2,999,065), sad-calcium acetate (USP2,999,066) and low-, in-, high molecular weight acids and oleic calcium salt of peach and soap.

Being used for the useful especially thickening material main character of grease composition is wetting ability, but be converted into and be the hydrophobic nature condition as just having introduced long chain hydrocarbon groups before the grease composition at them, for example use organic cation tensio-active agent (as compound) to carry out pre-treatment at surface of clay.Exemplary compounds be tetra-alkyl ammonium chloride (as dimethyl dioctadecyl ammonium chloride, dimethyl dibenzyl ammonium chloride and their mixture.This method for transformation is known in the art, believes to need not to do further discussion.More particularly, the clay that forms the useful raw material of thickening material that grease composition adopts can comprise natural chemically unmodified clay.These clays are crystalline composition silicates, because they are interior very on a large scale natural sources, their accurate composition is not described.These clays may be interpreted as compound inorganic metasilicate, as pure aluminium silicate, and Magnesium Silicate q-agent, barium silicate etc., they also contain the cation exchange group such as the sodium of variable quantity except lattice silicate.Can be transformed into the sticking polynite of useful especially hydrophilic clay bag of required thickening material, as wilkinite, attapulgite(U.S.'s activated clay), hectorite, illite, talcum powder, sepiolite, biotite, vermiculite, zeolite clay etc.The consumption of thickening material is that about 0.5-of total grease composition is about 30, preferred 3-15%(weight)

Lubricant and sense liquid are given an example:

Following example is in order to illustrate lubricant of the present invention and sense liquid composition.Numerical value all in the table I are all in weight percent.

The table I

Ⅰ??Ⅱ??Ⅲ??Ⅳ??Ⅴ??Ⅵ??Ⅶ??Ⅷ

Example 2 products 6-------

Example 3 products-6---6 66

Example 4 products--6-----

Example 5 products---6----

Example 6 products----6---

DMTD ^*On-the-spot

Preparation is with formaldehyde

Coupling in heptyl phenol 0.2 0.2 0.2 0.15 .20---

Ethyl propenoate/third

Olefin(e) acid 2-second is ester

Multipolymer .075 .075 .075 .075 .075 .075 .075 .075

Thinning oil .275 .275 .275 .275 .225 .225 .225 .225

Two uncle's nonyl DMTD-----0.35 0.10-

Single uncle's nonyl DMTD-------0.35

SAE80W-90

Base oil Rem ^*Rem Rem Rem Rem Rem Rem Rem

* be dimercaptothiodiazole

* is all the other

The prescription of example II, IV, V is tested with high torsional moment test of L-37 and the test of L-42 vibration at high speed.The L-37 test conditions is low speed, high moment of torsion, and estimates carrying capacity, wear-resisting stability and the corrosion resistance of gear grease.The L-42 test is an anti-wiping performance of evaluating EP additive in the gear lubricant under the vibration at high speed load.The prescription of example II, IV, V has passed through these tests.The result is as follows:

Example II example IV example V

L-37??Overall??2/0.51??2/1??2/1

L-42??Ring??2%??1%??3%

L-42??Pinion??2%??2%??5%

These results are significant, because lubricating composition prescription of the present invention was not thought by the necessary wear-resistant system of p and s alkene of two tests but do not contain in the prescription all by L-37 and L-42 test in the past.

The example IX

The lubricating composition that has prepared following prescription:

6.0%(weight) example 3 products; 0.20%(weight) on-site preparation and by the dimercaptothiodiazole of formaldehyde coupling in heptylphenol; 1.0%(weight) the esterification vinylbenzene-maleic anhydride copolymers of usefulness N-aminopropyl morpholine aftertreatment; 0.075%(weight) thinning oil; 0.35%(weight) oleyl amine; All the other are SAE 80W-90 base oil.

The example X

The lubricating composition that has prepared following prescription:

6.0%(weight) example 3 products; 0.20%(weight) on-site preparation and by the dimercaptothiodiazole of formaldehyde coupling in heptylphenol; 1.0%(weight) the esterification vinylbenzene-maleic anhydride copolymers of usefulness N-aminopropyl morpholine aftertreatment; 0.075%(weight) thinning oil; 0.25%(weight) C ₁₂Succsinic acid; All the other are the SAE80W-90 base oil.

The example XI

The lubricating composition that has prepared following prescription:

6.0%(weight) example 3 products; 0.20%(weight) on-site preparation and by the dimercaptothiodiazole of formaldehyde coupling in heptylphenol; 1.0%(weight) the esterification vinylbenzene-maleic anhydride copolymers of usefulness N-aminopropyl morpholine aftertreatment; 0.075%(weight) thinning oil; 0.030%(weight) monoisopropanolamine; All the other are the SAE80W-90 base oil.

The example XII

The lubricating composition that has prepared following prescription:

6.0%(weight) example 3 products; 0.20%(weight) on-site preparation and by the dimercaptothiodiazole of formaldehyde coupling in heptylphenol; 1.0%(weight) the esterification vinylbenzene-maleic anhydride copolymers of usefulness N-aminopropyl morpholine aftertreatment; 0.075%(weight) thinner; 0.10%(weight) 1-hydroxyethyl-2-heptadecene tetrahydroglyoxaline; 0.02%(weight) Tolad 7(Petrolite product is accredited as the polyethers that is dissolved in the aromatic solvent); All the other are SAE 80W-90 base oil.

Example X III

The lubricating composition that has prepared following prescription:

6.0%(weight) example 3 products; 0.20%(weight) on-site preparation and by the dimercaptothiodiazole of formaldehyde coupling in heptylphenol; 1.0%(weight) the esterification vinylbenzene-maleic anhydride copolymers of usefulness N-aminopropyl morpholine aftertreatment; 0.075%(weight) thinning oil; 0.20%(weight) ethoxyquin nonylphenol; All the other are the SAE80W-90 base oil.

Example X IV

The lubricating composition that has prepared following prescription:

6.0%(weight) example 3 products; 0.20%(weight) on-site preparation and by the dimercaptothiodiazole of formaldehyde coupling in heptylphenol; 1.0%(weight) the esterification vinylbenzene-maleic anhydride copolymers of usefulness N-aminopropyl morpholine aftertreatment; 0.075%(weight) thinning oil; 0.20%(weight) oleylamide; All the other are SAE 80W-90 base oil.

Example X V

The lubricating composition that has prepared following prescription:

6.0%(weight) example 3 products; 0.20%(weight) on-site preparation and by the dimercaptothiodiazole of formaldehyde coupling in heptylphenol; 1.0%(weight) the esterification vinylbenzene-maleic anhydride copolymers of usefulness N-aminopropyl morpholine aftertreatment; 0.075%(weight) thinning oil; 0.050%(weight) polyglycol 112-2(Dow Chemical product is accredited as ethoxyquin-third oxide diol); All the other are SAE 80W-90 base oil.

Example X VI

The lubricating composition that has prepared following prescription:

6.0%(weight) example 3 products; 0.20%(weight) on-site preparation and by the dimercaptothiodiazole of formaldehyde coupling in heptylphenol; 1.0%(weight) the esterification vinylbenzene-maleic anhydride copolymers of usefulness N-aminopropyl morpholine aftertreatment; 0.075%(weight) thinning oil; 0.05%(weight) Pluronic L101(Wyandotte product is accredited as poly-(third oxygen-ethoxy) ethanol); All the other are SAE 80W-90 base oil.

Example X VII

The lubricating oil composition that has prepared following prescription:

3.0%(weight) example 5 products; 3.0%(weight) example A-54 product; 0.15%(weight) on-site preparation also uses the formaldehyde coupling in the dimercaptothiodiazole of heptylphenol; 0.75%(weight) ethyl propenoate and vinylformic acid-2-b hexyl; 0.275%(weight) thinning oil; All the other are SAE 80W-90 base oil.This prescription is tested with L-37 and L-42 method, and the result is all by test:

L-37??2/0.51

L-42??Ring??0%

L-42??Pinion??1%

Example X VIII-X XI

Prepared following tractor hydraulic fluid (all numerical value are all represented with weight percent):

ⅩⅦ??ⅩⅨ??ⅩⅩ??ⅩⅪ

Example 2 products 3.00---

Example 3 products-3.00--

Example 22 products--3.00-

Example 26 products---3.00

Vinylbenzene-maleic anhydride

Multipolymer is through C ₄-

₁₈The alcohol esterification, aminopropyl

The morpholine aftertreatment, and

Contain sterically hindered phenolic antioxidant 6.60 6.60 6.60 6.60

Esterification-maleic anhydride copolymerization

Thing is through aminopropyl morpholine

Aftertreatment 0.30 0.30 0.30 0.30

Siloxanes kilfoam 0.02 0.02 0.02 0.02

Base oil (60%60

-70N,30%

160N,10%

Cycloalkanes 60N) 90.08 90.08 90.08 90.08

Example X XII

The lubricating oil composition that has prepared following prescription:

3%(weight) example 3 products; The zinc salt of phosphorodithioic acid 2.7%(weight) (producing) with Vanadium Pentoxide in FLAKES and 60mole%4-methyl-2-amylalcohol and the reaction of 40mole% isopropanol mixture; 1%(weight) high-alkali fatty acid calcium; 0.2%(weight) Duomeen T(Akzo product is accredited as N-tallow triethylenediamine); 0.075%(weight) siloxanes kilfoam; 0.0225%(weight) thinning oil; All the other are SAE 80W-90 base oil, and the copper bar of this prescription is assessed as 130,100 ℃ of 1A(ASTM D)

Example XX III

The cutting fluid that has prepared following composition:

Weight %

Example 5 products 5

100 neutral base oils 95

(tapping test) number 035.003.04 carries out the test of this cutting fluid with the tapping test, obtains following result:

Tapping efficient %

The mild steel stainless steel

148??112

Fuel composition:

Fuel composition of the present invention contains the conventional liq fuel of main per-cent, petroleum fractions hydrocarbon matter fuel normally, as ASTM specification sheets motor spirit that D439 decides and ASTM specification sheets D396 fixed diesel-fuel or oil fuel.The conventional liq fuel composition comprises the nonhydrocarbon metallic substance, as deriving from the liquid fuel of plant or mineral sources (as Zea mays, clover, shale and coal), all is within the scope of the invention as (for example methyl alcohol, ethanol, ether, methyl ethyl ether, Nitromethane 99Min.s) such as alcohol, ether, organic nitro-compounds.

The conventional liq fuel of one or more hydrocarbon matter fuel and one or more nonhydrocarbon metallic substance mixtures also is admissible.The example of such mixture has the combination of gasoline and ethanol and diesel-fuel and ether.Particularly preferably be gasoline, it is the hydrocarbon mixture of ASTM boiling range from about 60 ℃ (distillation end points 10%) to about 205 ℃ (distillation end points 90%).

Generally, these compositions contain the sulfuration high alkalinity product of the present invention that improves the character amount.This measures normally per 1,000,000 parts of about 50,000 weight parts of the about 1-of fuel, the high alkali product of sulfuration of about 5000 weight parts of preferably about 4-.

Except composition of the present invention, fuel composition can contain other additive well known to those skilled in the art.They are octane promoters, as lead tetraalkyl; Plumbous scavenging agent is as haloalkane (for example ethylene dichloride, ethylene dibromide); Resistance depressant prescription or properties-correcting agent such as tricresyl phosphate alkane ester, dyestuff, n-Hexadecane properties-correcting agent, antioxidant such as 2,6 di tert butyl 4 methyl phenol; Rust-preventive agent such as alkylated succinic acid and acid anhydride; Fungistat; Press down jelly; Metal deactivator; Emulsion splitter; Frostproofer.

Water-oil emulsion, water base concentrated solution and water-based functional fluid's body:

The present invention also comprises the water-oil emulsion that contains sulfuration high alkalinity product of the present invention, water base concentrated dense and water-based functional fluid's body.Water-fat liquor can be water-in-oil or O/w emulsion, and " oil-in-water " emulsion (being abbreviated as " O/W ") refers to that the external phase in the emulsion is water, and discontinuous phase is an organic substance, and discrete organic phase is scattered in the successive aqueous phase.Concentrated solution generally contains the about 80%(weight of about 20-) water.The general moisture 80%(weight that surpasses of water-based functional fluid's body).It is about 0.05% that water-fat liquor and water-based functional fluid's body generally contain, about 20%(weight) the present invention vulcanize the high alkalinity product.Water-fat liquor generally contains the about 80%(weight of about 1%-) water and the about 99%(weight of about 20%-) oil.It is about 15% that the general oil-containing of water-based functional fluid's body is lower than, and preferably is lower than approximately 5%, preferably is lower than about 2%.Operable oil is described in above-mentioned " natural and synthetic oil " one the joint among.

These emulsions, enriched material and water-based functional fluid's body can also comprise other conventional additives that adopts in be everlasting water-fat liquor and the water-based functional fluid's body, and they comprise emulsifying agent, dispersion agent, tensio-active agent, thickening material, molten and water-soluble functional additive of oil such as anti-wear agent, extreme pressure agent etc. and supplemented by additives such as stopping agent, the shear stable agent, sterilant, dyestuff, water-softening agent, cover smelly dose, kilfoam etc.

Concentrated solution is similar to emulsion and water-based functional fluid's body except that containing less water and containing other more component on ratio.Dilute with water can be transformed into concentrated solution emulsion or water-based functional fluid's body.Dilution working standard hybrid technology.This usually is a method easily, because concentrated solution can be transported to the use point before thin up, can save the trucking costs that is used for the used big water gaging of final emulsion and water-based functional fluid's body, the required water of the just concentrated solution preparation of transporting factor decisions such as (mainly by) being easy to handle and convenient.

Generally, emulsion and water-based functional fluid's preparation is the dilute with water concentrated solution, and the ratio Chang Weiyue of water and concentrated solution 1: 100 is to about 100: 1(weight).

In one embodiment, water-based functional fluid's body is the solution form, and is micella dispersion or the microemulsion that looks like true solution in another embodiment.Solution, the formation of micella dispersion liquid or microemulsion depends on the individual components that is adopted especially.

The present invention also comprises emulsion, concentrated solution and the water-based functional fluid's of water-fat liquor, normal other conventional additives that adopts of water-based functional fluid's body preparation method, and these methods comprise the following steps:

(1) simultaneously or mix successively to form dispersion liquid or solution with other conventional additives of sulfuration high alkalinity product of the present invention and these; All right

(2) in this dispersion liquid or solution, add water (can also add the oil for preparing emulsion) to form said concentrated solution; And/or

(3) water (can also add the oil for preparing emulsion) dilutes this dispersion liquid or solution or concentrated solution, and the total amount that adds entry should provide the required amount of component of the present invention and other functional additive desired concn in this concentrated solution or emulsion or the water-based functional fluid's body.

These mixing steps preferably carry out with conventional equipment, generally in room temperature to slightly high temperature, normally be lower than 100 ℃, often be lower than 50 ℃.On point out that concentrated solution can be transported to the use point after formation, water (can also with oil) dilution forms required emulsion or water-based functional fluid's body again.Be that forming final emulsion or water-based functional fluid's body can carry out in forming the used same equipment of concentrated solution or dispersion liquid or solution at some other example.

Useful dispersion agent or emulsifying agent comprise in the following patent nitrogenous without phosphorus carboxylic acid stabilized dose among the present invention: USP4,329,249; 4,368,133; 4,435,297; 4,447,348 and 4,448,703, reference now is provided.In brief, the preparation of these dispersion agents is that (I) contained the alkyl that at least a carboxylic acid acylating agent that at least one carbonatoms replaces for the hydrocarbon of about 12-about 500 and (II) at least a (a) N-(hydroxyl replace) many-oxyls (a) amine analogue of amine, the replacement of (b) hydroxyl or (c)-(a)+(b) mixture.Preferred acylating agent comprises the amber acid or anhydride of replacement.Preferred amine comprises one-level, secondary and three grades of alkanolamines or their mixture.These dispersion agents preferably use with the significant quantity that can disperse or dissolve the functional additive in concentrated solution, emulsion and/or the water base functional liquid that various additives, particularly the present invention be discussed below.Dispersion agent is the succinyl oxide of polyisobutenyl (n=950) replacement and the reaction product of diethylethanolamine in one embodiment.

Useful tensio-active agent can be cationic, anionic, non-ionic or amphoteric typical.Many tensio-active agents in all types of all are as known in the art." Emulsifiers ﹠amp referring to for example McCutcheon; Detergents ", 1981, North American Edition, McCutcheon Division, MC Publishing Co. publishes, Glen Rock, New Jersey, U.S.A..Provide reference at this.

Nonionic surface active agent is the product that alkylene oxide is handled, as alcohol, phenol, ester, amine and the acid amides of alkylene oxide processing.Ethylene oxy/propylene oxygen segmented copolymer also is useful nonionic surface active agent.Glyceryl ester and sugar ester also are known as tensio-active agent.The non-ionic type class tensio-active agent that is used for a quasi-representative of the present invention is the alkylphenol that alkylene oxide is handled, as Rohm ﹠amp; Haas Co.The alkylene oxide alkylphenol condensation of selling.Its specific examples is Triton X-100, and per molecule contains a 9-10 ethylene oxide unit, and the HLB value is about 13.5, and molecular weight is about 628.Also have many known nonionic surface active agent that other is fit to.Referring to the works of for example above-mentioned McCutcheon and the disquisition of Martin J.Schick " Non-Ionic Surfactants ", M.Dekker Co., New York, 1967.At this as a reference.

On address, positively charged ion, negatively charged ion and amphoterics also are operable.They generally all are the hydrophilic surfactant actives.Anion surfactant contains the negative charge polar group, and cats product contains the positive charge polar group, and amphoteric dispersant contains two types polar group in a part.The general knowledge of useful tensio-active agent is found in " Kirk-Othmer Encyclopedia of Chemical Technology ", second edition Vol.19, P.507 play (1969, John Wiley and Son, New York) and the above-mentioned publication published of McCutcheon, in this reference as positively charged ion, both sexes and aniorfic surfactant.

The aniorfic surfactant of extensively knowing is a carboxylic soap, organic sulfate, sulfonate, sulphonyl carboxylic acid and salt thereof and phosphoric acid salt.Useful cats product comprises nitrogen compound, the oxide compound of amine and the quaternary ammonium salt of knowing.Amphoterics comprises amino acid pattern compound and similar type.Various positively charged ions, negatively charged ion and amphoteric dispersant all have the industry supply, and particularly the company by the U.S. supplies, as Rohm ﹠amp; Haas and Union Carbide Corp. also are found in " Anionie Surfactants " II and III part of W.M.Linfield about the further situation of positively charged ion and anion surfactant, Marcel Dekker, Inc. publish, New York, 1976 and E.Jungermann, " Cationic Surfactants ", Marcel Dekker, Inc.，New??York，1976。Be made for reference at this.

When using these tensio-active agents, the general significant quantity that can help to disperse various additives, particularly functional additive to be discussed below in concentrated solution of the present invention, emulsion and the water-based functional fluid's body that adopts.Enriched material preferably contains up to about 75%, preferred about 10% to about 75%(weight) one or more these tensio-active agents.Emulsion and water-based functional fluid's body can contain up to about 15%, preferred about 0.05% to about 15%(weight) one or more these tensio-active agents.

Emulsion of the present invention and water-based functional fluid's body often contain the thickening combination of at least a thickening material.Thickening material generally can be polysaccharide, synthetic polymer or their two or more mixtures.Useful polysaccharide is a natural gum, and is disclosed among " Industrial Gums " (the Academic Press, nineteen fifty-nine publishes) as Whistler and B.Miller.The related water-soluble thickening natural gum of this book is provided in that this is for reference.This type of gummy object lesson is agaropectin, guar gum, gum arabic, alginic acid, dextran, flaw in a piece of jade xanthan etc.The polysaccharide that acts on the useful thickening material of aqueous composition of the present invention is ether of cellulose and ester, comprises hydroxy alkylene Mierocrystalline cellulose and alkyl hydroxylated cellulose and their salt.The object lesson of this thickening material is Natvosol and sodium carboxymethyl-cellulose.Two or more mixtures of this thickening material also are useful.

In one embodiment, require thickening material can be dissolved in the water of cold (10 ℃) and heat (about 90 ℃).This does not comprise the material as methylcellulose gum and so on, and it only is dissolved in cold water, is insoluble to hot water.But this material that is insoluble to hot water can be used to increase other function, as oilness is provided.

These thickening materials also can be synthetic thickening polymers.Many is known in the art, its representative is polyacrylic ester, polyacrylamide, hydrolysis of vinyl ester, contain 50 moles of % acrylamido alkyl sulfonic acid ester and other comonomer such as vinyl cyanide at least, the water-soluble homopolymerization of acrylamido alkyl sulfonic acid ester and the multipolymer of vinylbenzene etc.Poly--the n-vinyl pyrrolidone, styrene homopolymers and multipolymer and cinnamic water-soluble salt, maleic anhydride and iso-butylene maleic anhydride copolymers also can be used as thickening material.

Other useful thickening material is known in the art, many publications " Functional Materials " of all listing in above-mentioned McCutcheon (1976, PP.135-147) in.The water soluble polymeric viscosifiers that its disclosure relates to meets above-mentioned total requirement, provides reference at this.

Useful thickening material, particularly require can be stable under high shearing is used the present composition time, be the reaction product of water-dispersion, this product is by at least a hydrocarbyl substituted succinic and/or by formula

The end capped polyoxyalkylene of amine of acid anhydride of representative (R is the alkyl of about 40 carbon atoms of about 8-in the formula) and at least a water-dispersion or the hydroxy-end capped polyoxyalkylene reaction of at least a water-dispersion form.R preferably about 8 is more preferably about 12 to about 24 carbon atoms to about 30 carbon atoms, and particularly about 16 to about 18 carbon atoms.In a best specific embodiments, R is by formula

Representative, R ' and R in the formula " be independently hydrogen or straight chain or straight-chain alkyl basically, condition be among the R the total number of carbon atoms in above-mentioned stated limit.R ' and R " preferably alkyl or alkenyl.In a good especially specific embodiments, the carbonatoms of R is about 16 to about 18, and R ' is hydrogen or 1 alkyl or 2 alkenyls to about 7 carbon atoms to about 7 carbon atoms, and R " is alkyl or about 5 alkenyls to about 15 carbon atoms.

The amine end-blocking polyoxyalkylene of water-dispersion is α preferably, Ω-diamino polyoxyalkylene.α, Ω-diamino polyoxytrimethylene polyoxyethylene polyoxytrimethylene or α, the end capped polyoxyethylene of Ω-diamino third alkylene oxide.The end capped polyoxyalkylene of amido also can be polyamines base (for example three amidos, tetramine base an etc.) polyoxyalkylene, as long as it is the end capped and water dispersible of amido.

The water dispersible amine end capped polyoxyalkylene useful in the present invention is disclosed in USP3,021,232; 3,108,011; In 4,444,566 and Re31,522, now provide reference.The useful end capped polyoxyalkylene of water dispersible amine, Texaco Chemieal Co. have the industry supply, and its commodity are called Jeffamine.

The hydroxy-end capped polyoxyalkylene of water dispersible is the block polymer of third alkylene oxide and ethylene oxide, and the core of the organic compound of the self-contained many reactive hydrogen atoms of deriving is arranged.Block polymer is connected the reactive hydrogen place on the core.The example of these compounds comprises the hydroxy-end capped polyoxyalkylene with the following formula representative.

A and b are integers in the formula, and the molecular weight that this number makes the propylene oxide chain makes the ethylene oxide chain constitute about 20% to about 90%, preferred about 25% to about 55% of compound weight between about 900 to about 25,000.These compd Bs ASF Wyandotte Corp. has the industry supply, and its commodity are called " Tetronic ".Other example comprises the hydroxy-end capped polyoxyalkylene with the following formula representative.

HO（C ₂H ₄O） _x（C ₃H ₆O） _y（C ₂H ₄O） _zH

Y is an integer in the formula, makes the molecular weight of propylene oxide chain be at least about 900; X and Z are integers, make the ethylene oxide chain constitute about 20% to about 90% of compound weight.These compounds preferably have about 1100 molecular weight to about 14,000 scopes.These compd Bs ASF Wyandotte Corp. has the industry supply, and its commodity are called " Pluronic ".Useful hydroxy-end capped polyoxyalkylene is disclosed in USP2, in 674,619 and 2,979,528, provides reference at this.

Reaction between the end capped or hydroxy-end capped polyoxyalkylene of carboxylic acid reagent and amine can be carried out to the lowest decomposition temperature scope of reactant or product at the high melting temperature of reactant.Generally, reaction is to carry out between about 60 ℃ to about 160 ℃.The equivalence ratio of carboxylic acid reagent and polyoxyalkylene preferably about 0.1: 1 to about 8: 1, preferred about 1: 1 to about 4: 1, particularly about 2: 1.The amount of the carboxylic acid reagent of monovalent can be removed its molecular weight determination with carboxylic acid function's number.The weight of the end capped polyoxyalkylene of amine of monovalent can be removed its molecular weight with the amino number of end and measure.The weight of the hydroxy-end capped polyoxyalkylene of monovalent can be removed its molecular weight with the terminal hydroxy group number and measure.End amido and terminal hydroxy group number can be measured or be measured by the empirical method of knowing usually by the structural formula of polyoxyalkylene.Acid amides/acid and ester/acid that carboxylic acid reagent and amine end-blocking or hydroxy-end capped polyoxyalkylene reaction form can neutralize with for example one or more basic metal, one or more amine or their mixture, and they are changed into acid amides/salt or ester/salt respectively.In addition, as concentrated solution or functional liquid with these acid amides/acid or ester/acid adding alkali metal containing or amine, acid amides/salt or ester/salt often can form on the spot.

Now with U.S. Pat P4,659,492; 4,664,834; 4,661,275 and 4,749,500 are provided in this carries out reference for using when alkyl replaces amber acid or anhydride/hydroxyl or amine end-blocking polyoxyalkylene reaction product as thickening material in water composition.

When forming thickening material with the end capped polyoxyalkylene of amine, this thickening material characteristic can increase at least a tensio-active agent therein and improve.Any tensio-active agent in subhead " Surfactants " all can be made this use.During use, the ratio of thickening material and tensio-active agent is generally at about 1: 5 to about 5: 1, preferred about 1: 1 to about 3: 1.

Generally, the amount of thickening material in water composition is the thickening amount.When using, thickening material is preferably in and reaches the about 70% of concentrated solution of the present invention, and preferred about 20% to about 50%(weight) level.In sense liquid of the present invention, the amount of thickening material is preferably in about 1.5% to about 10% scope of functional liquid body weight, and preferred about 3% to about 6%.

The functional additive that uses in water-fat liquor and water-based functional fluid's body is typical oil soluble and water-soluble additive, they in conventional oil based system as extreme pressure agent, anti-wear agent, load agent, dispersion agent, friction modifying agent, lubricant etc.They also can be used as slipproofing agent, membrane-forming agent and friction modifying agent.As knowing, these additives can have one or more above-mentioned purposes, and for example the extreme pressure agent is commonly used for load agent.

" molten, the water-insoluble functional additive of oil " speech refers to that this functional additive water-fast level in the time of 25 ℃ restrains but the dissolution degree in mineral oil whenever rises to few 1 in the time of 25 ℃ more than about 1 gram of per 100 ml waters.

Functional additive also can comprise some solid lubricant, as graphite, molybdenum two sulphur and tetrafluoroethylene and relevant solid polymer.

These functional additives also can comprise the agent of friction polymer formation.In brief, they are materials that potential forms polymkeric substance, are scattered in the liquid vehicle and in friction or surface in contact with lower concentration polymerization is formed lip-deep protection polymeric membrane.Believe that polymerization is the result of the chemical action on hot or possible catalysis that produces and/or the surface that newly exposes that rubs.The specific examples of this material is the combination of dilinoleic acid and ethylene glycol, and they have formed polyester friction polymeric membrane.These materials are known in the art and narrate in following publication, " Wear " Vol.26 for example, PP369-392; No. 2,339,065, Deutsches Reichs-Patent application is in this reference as discussion friction polymer formation thing.

These typical functional additives are known organosulfurs, phosphorus, and the metal of boron or carboxylic acid or amine salt, they are identical or same type with the functional additive that is used for oil-based fluid.The carboxylic acid that typical this salt is 1-22 carbon atom (comprising aromatics and aliphatic carboxylic acid) salt, the salt of sulfur acid such as alkyl and aromatic sulfonic acid etc., phosphoric acid such as phosphoric acid, phosphorous acid, phosphonous acid, phosphate ester acid and similar sulphur homologue such as thiophosphoric acid, phosphorodithioic acid and relevant acid esters, boronic acid containing such as boric acid, biborate etc.Useful functional additive also comprises dithiocarbamic acid metal-salt such as molybdenum salt and antimonic salt, dibutyltin sulfide, tributyltin oxide, phosphoric acid salt and phosphite, the ammonium salt of boric acid, clorafin, trialkyl stannic oxide, molybdenum phosphate and clorafin.

Many these type of functional additives are known in the art.For example useful additive is described in " Advances in Petroleum Chemistry and Refining " in conventional oil based system and aqueous based systems of the present invention, Vol.8.John.J.Mcketta compiles, Imterscience Publishers, New York, 1963, PP.31-38; Kirk Othmer, " Encyclopedia of Chemical Technology ", Vol.12,2nd Ed., Intersciences Publishers, New York, 1967, P.575 rise; M.W.Ranney, " Lubricant Additives ", Noyes Data Corp., Park Ridge, N.J., USA, 1973; C.V.Smalheer and R.K.Smith, " Lubricant Additives ", The Lezius-Hiles Co., Cleveland, Ohio, USA.These documents provide the reference of functional additive useful in the present composition.

In one embodiment, functional additive is sulphur or the agent of chloro-sulphur extreme pressure, and is known useful in oil based system.This material comprises chlorinated aliphatic such as clorafin, organic sulfide and polysulfide such as benzyl disulfide, two (benzyl chloride base) two sulphur, dibutyl four sulphur, the sulfuration Sperm whale oil, sulfuration Witconol 2301, sulphurized alkyl phenols, the sulfuration limonene, sulfuration terpenes and sulfuration Diels-Alder adducts, the reaction product of phosphosulfurized hydrocarbon such as phosphoric sulfide and turps or Witconol 2301, the ester of phosphoric acid (is a dibutyl phosphite as two hydrocarbon or trialkyl phosphorous acid ester, phosphorous acid two heptyl esters, phosphorous acid two cyclohexyls, phosphorous acid amyl group phenyl ester, phosphorous acid diamyl phenyl ester, tridecyl phosphite, the phenol phosphorous acid ester that phosphorous acid distearyl ester and many propylidene replace); Thiocarbamate metal-salt such as dioctyl zinc dithiocarbamate, heptylphenol dithiocarbamic acid barium; And the II family metal-salt of phosphorodithioic acid such as cyclohexyl zinc dithiophosphate.

Functional additive also can be a film forming agent, as synthetic or natural emulsion or their suspension in water.Such latex comprises caoutchouc latex and polystyrene/divinyl synthetic latex.

Functional additive also can be antidetonation or anti-tick.The former example is that acid amides/phosphorodithioic acid metal-salt combination is (as Deutsches Reichs-Patent 1,109, disclosed in No. 302), amine salt/azomethine combination is (as british patent specification 893, disclosed in 977) or amine/dithiophosphates (as United States Patent (USP) 3, disclosed in 002,014).The example of anti-tick have N-acyl group sarkosine and derivative thereof (as United States Patent (USP) 3,156,652 and 3; 156; disclosed in 653), sulfurized lipid acid and ester thereof are (as United States Patent (USP) 2,913; 415 and 2; 982,734 is disclosed), the ester of dimer (fatty acid) yl is (as United States Patent (USP) 3; disclosed in 039,967).Above-mentioned patent is provided in this as the reference that is used for emulsion of the present invention and water-based functional fluid's body functional additive.

What generally, add in emulsion of the present invention and water-based functional fluid's body is the functional additive of sense significant quantity." sense significant quantity " refers to because the adding of this additive makes the q.s that produces desired properties.For example, if additive is a rust-preventive agent, its sense significant quantity is the amount that is enough to increase the rust-preventing characteristic of the composition that is added.Equally, if anti-wear agent, then the anti-wear agent of sense significant quantity is the amount that is enough to improve this anti-wear agent of the composition antiwear characteristics that is added.

Emulsion of the present invention or water-based functional fluid's body often contain at least a anticolodal.These sanitass can stop ferrous metal or non-black metal (for example copper, brass, bronze, titanium, aluminium etc.) or the corrosion of the two amine.Sanitas can be an organic or inorganic, normally fill part water-soluble so that satisfied preservative activity to be provided, though they do not need water-solublely just anti-corrosion function can be arranged.The many inorganic corrosion inhibitor that are suitable in aqueous systems of the present invention are well known by persons skilled in the art, it comprise Burns and Bradley's " Proteetive Coatings for Metals ", the 13rd chapter, PP.596-605(Reinhold Publishing Corp., second edition) sanitas described in.At this as a reference.The object lesson of inorganic corrosion inhibitor comprises nitrite alkali metal-salt, two-and tripolyphosphate sodium salt, potassium phosphate salt and di-potassium, boric acid base metal-salt and their mixture.Many suitable organic anti-corrosive agent are well-known to those skilled in the art, specific examples comprises the alkylamine neutral acid that alkylamine and hydroxyl replace, and for example contains the lipid acid of about 22 carbon atoms of about 8-as neutral phosphoric acid salt and alkyl phosphate, neutral lipid acid), neutral aromatic acid (for example 4-p t butylbenzoic acid), neutral naphthenic acid and neutral hydrocarbyl sulfonate.The mixing salt ester of the inferior acid amides of alkylation amber also is useful.Useful especially amine comprises alkanolamine, as thanomin, diethanolamine.Any above-mentioned two or more sanitass also are operable.Sanitas in concentrated solution uses and can prevent that the metal that contacts with water composition from producing the corrosive significant quantity.

Some emulsion of the present invention and water-based functional fluid's body (particularly those are used to cut or metal forming) also can contain at least a opposite water miscible polyvalent alcohol that has, and solubleness was less when this polyvalent alcohol rose in water temperature.Therefore they can be used as the surface lubricant that smear metal or work add man-hour, because when metal works and machining tool friction, liquid has been heated, and has the polyvalent alcohol of opposite solubleness just to be attached to the surface of work, thereby has improved its lubricating property.

Emulsion of the present invention and water base functional liquid also can comprise at least a sterilant, this sterilant is well known to those skilled in the art, and " Functional Materials " 9-20 page head that its specific examples is found in above-mentioned McCutcheon is " Antimicrobials ".Be used for the reference of the suitable sterilant of water composition of the present invention or system in this conduct.Generally, this sterilant is water miscible, is to a certain degree water-soluble to play a germicidal action at least.

Emulsion of the present invention and water-based functional fluid's body also can comprise other material, as dyestuff (for example acid green dyestuff), water-softening agent (for example disodium edta or itrile group nitrilotriacetic) is covered smelly dose (for example lemongrass, lemon wet goods) and kilfoam, siloxanes kilfoam as the well-known.

Emulsion of the present invention and water-based functional fluid also can comprise antifreeze additive, so that use composition at low temperature, can be used as frostproofer as ethylene glycol and similar polyoxyalkylene polyol.Very clear, its consumption is decided by the degree of anti-frost protection, and this is known to one of ordinary skill in the art.

Should be noted also that the many above-mentioned production emulsions of the present invention and the composition of water-based functional fluid's body and function all are Industrial products, they have presented more than one character to this emulsion and water-based functional fluid's body.Therefore only just can provide several functions with a kind of composition, from the needs of cancelling or reduced some other supplementary component.The extreme pressure agent that for example resembles tributyltin oxide and so on also can be used as sterilant.

The present invention is illustrated with its best specific embodiments, but must understand, and various changes or the modification made according to specification sheets of the present invention will be clearly for those skilled in the art.Therefore, should be understood to this change or the modification of having covered disclosed in this invention, they fall into the scope of appended claim.

Claims

1, a kind of composition, said composition comprise at least a sulfuration high alkalinity product, and the preparation of this product is that the high alkalinity product with (A) at least a high alkalinity product or (A ') at least a boracic contacts with (B) sulphur and/or at least a sulphur source;

This high alkalinity product (A) and boracic high alkalinity product (A ') are that (condition is that these acidic substance are not SO with at least a acidic substance ₂Or SO ₂The source) prepares; SO with this high alkalinity product (A) or boracic high alkalinity product (A ') and significant quantity ₂Or SO ₂The source contact is to replace the part acid material.

2, the composition of claim 1, wherein said high alkalinity product (A) or boracic high alkalinity product (A ') with before component (B) contacts with said SO ₂Or SO ₂The source contacts.

3, the composition of claim 1, wherein said high alkalinity product (A) or boracic high alkalinity product (A ') while and component (B) and said SO ₂Or SO ₂The source contact.

4, the composition of claim 1, the preparation of wherein said high alkalinity product (A) or boracic high alkalinity product (A ') is by the organic substance (A) (I) and the reaction medium (A) (II) of high alkalization with at least a, this organic substance that is alkalized by height (A) (I) is dissolved in this reaction medium (A) (II), is a kind of carboxylic acid or anhydride with the following formula representative at least:

R is an alkyl in the formula.

5, the composition of claim 1, wherein said high alkalinity product (A) or boracic high alkalinity product (A ') are to be prepared by the organic materials (A) (I) of high alkalization and a reaction medium (A) (II) with at least a, said organic substance by high alkalization is dissolved in the said reaction medium (A) (II), and be the amber acid or anhydride of at least a replacement, said replacement amber acid or anhydride is made up of substituting group and amber acidic group, wherein substituting group is derived from polyolefine, and the feature of acid or anhydride is whenever on average have an appointment at least 0.9 amber acidic group of the heavy substituting group of amount in its structure.

6, the composition of claim 1, wherein said high alkalinity product (A) or boracic high alkalinity product (A ') are to be prepared by the organic materials (A) (I) of high alkalization and a reaction medium (A) (II) with at least a, said organic substance by high alkalization is dissolved in the said reaction medium (A) (II), and be the amber acid or anhydride of at least a replacement, said replacement amber acid or anhydride is made up of substituting group and amber acidic group, wherein substituting group is derived from polybutene, wherein at least about 50% derived from total unit of butylene derived from iso-butylene, the feature of said polybutene is that its Mn is about 1500 to about 2000, Mw/ Mn value is about 3 to about 4, the feature of said acid or anhydride be in its structure whenever the heavy substituting group on average about 1.5 of amount to about 2.5 equivalent amber acidic groups.

7, the composition of claim 1, wherein said high alkalinity product (A) or boracic high alkalinity product (A ') are to be prepared by the organic materials (A) (I) of high alkalization and a reaction medium (A) (II) with at least a, said organic substance by high alkalization is dissolved in the said reaction medium (A) (II), and be the amber acid or anhydride of at least a replacement, said replacement amber acid or anhydride is made up of substituting group and amber acidic group, wherein substituting group is derived from polybutene, wherein at least about 50% derived from total unit of butylene derived from iso-butylene, the feature of said polybutene is that its Mn value is about 800 to about 1200, Mw/ Mn value is about 2 to about 3, the feature of said acid or anhydride be in its structure whenever the heavy substituting group on average about 0.9 of amount to about 1.2 equivalent amber acidic groups.

8, the composition of claim 1, wherein said high alkalinity product (A) or boracic high alkalinity product (A ') are to be prepared by the organic materials (A) (I) of high alkalization and a reaction medium (A) (II) with at least a, said organic substance by high alkalization is dissolved in the said reaction medium (A) (II), and by the following formula representative

R in the formula ¹, R ², R ³, R ⁴, R ⁵, R ⁶Be independently hydrogen or alkyl; R ²And R ³Can be joined together to form alicyclic ring or aromatic ring; A is the section of 0-about 4.

9, the composition of claim 1, wherein said high alkalinity product (A) or boracic high alkalinity product (A ') are to be prepared by the organic materials (A) (I) of high alkalization and a reaction medium (A) (II) with at least a, said organic substance by high alkalization is dissolved in the said reaction medium (A) (II), and is representative with the following formula:

R in the formula ¹And R ²Be aliphatic hydrocarbyl, a and b are the integers of 0-5, and condition is that a+b is no more than 5, and c is the number of 0-4.

10, the composition of claim 1, wherein said high alkalinity product (A) or boracic high alkalinity product (A ') are to be prepared by the organic materials (A) (I) of high alkalization and a reaction medium (A) (II) with at least a, said organic substance by high alkalization is dissolved in the said reaction medium (A) (II), and be a compound at least with the following formula representative

R is an aliphatic hydrocarbyl in the formula, and Ar is an aryl, X ¹And X ²Be independently oxygen or sulphur, a is the number of 0-about 4, and b is the number of 1-about 4, and condition is that a+b is no more than the number of replacing hydrogen on virtue nuclear or the Ar nuclear.

11, the composition of claim 1, wherein said high alkalinity product (A) or boracic high alkalinity product (A ') are to be prepared by the organic materials (A) (I) of high alkalization and a reaction medium (A) (II) with at least a, said organic substance by high alkalization is dissolved in the said reaction medium (A) (II), and be a compound at least with the following formula representative

R is an aliphatic hydrocarbyl in the formula, aryl among the Ar, X ¹, X ²X ³Be independently oxygen or sulphur, a is the number of 0-about 4, and b is the number of 1-about 4, and c is the number of 1-about 4, and condition is that a+b+c is no more than the number of replacing hydrogen on virtue nuclear or the Ar nuclear.

12, the composition of claim 1, wherein said high alkalinity product (A) or boracic high alkalinity product (A ') are to be prepared by the organic materials (A) (I) of high alkalization and a reaction medium (A) (II) with at least a, said organic substance by high alkalization is dissolved in the said reaction medium (A) (II), and is a compound with the following formula representative at least:

R is an aliphatic group in the formula, and a is the number of 0-about 4, and b is the number of 1-about 4, and c is the number of 1-about 4, and condition is that a+b+c is no more than 6.

13, the composition of claim 1, wherein said high alkalinity product (A) or boracic high alkalinity product (A ') are to be prepared by the organic materials (A) (I) of high alkalization and a reaction medium (A) (II) with at least a, said organic substance by high alkalization is dissolved in the said reaction medium (A) (II), and is monosulfonic acid, thionamic acid, thiosulfonic acid,-sulfinic acid, sulfenic acid, sulfuric acid part ester, thiosulfuric acid or hyposulfurous acid at least.

14, the composition of claim 1, wherein said high alkalinity product (A) or boracic high alkalinity product (A ') are to be prepared by the organic materials (A) (I) of high alkalization and a reaction medium (A) (II) with at least a, said organic substance by high alkalization is dissolved in the said reaction medium (A) (II), and is at least one compound with the following formula representative:

(R _a-T-(SO ₃) _b) _cM _dOr (R-(SO ₃) _b) _cM _d

R is an aliphatic group in the formula, and T is a cyclic hydrocarbon radical, and M is hydrogen or metallic cation, and a, b, c, d respectively are at least 1.

15, the composition of claim 1, the preparation of wherein said high alkalinity product (A) or boracic high alkalinity product (A ') is by the organic materials of high alkalization with at least a, said organic materials by high alkalization is selected from one or more following acid or its metal-salts: mahogany acid, heavy sulfonic acid, derived from Saybolt viscosity is the sulfonic acid of the lubricating oil distillate of about 100 seconds (100)-Yue 200 seconds (210), vaseline sulfonic acid, sulfonic acid and polyphenyl that single and many waxes replace, naphthalene, phenol, phenyl ether, naphthyl disulfide, pentanoic, the sulfonic acid of thiophene phenol or α-Lv Dainai, C ₄-C ₄₀Alkyl benzene sulphonate (ABS), hexadecyl phenol list sulfide sulfonic acid, two (hexadecyl) sulfo-anthrene disulfonic acid, dilauryl-betanaphthyl sulfonic acid and two decanoyl nitro-naphthalene-monosulfonic acids.

16, the composition of claim 1, wherein overbasic product (A) or boracic high alkalinity product (A ') are to be prepared by the organic materials of high alkalization with at least a, said organic materials by high alkalization is selected from a kind of following acid or metal-salt that should acid: paraffinic hydrocarbon sulfonic acid, unsaturated paraffinic hydrocarbon sulfonic acid, the paraffinic hydrocarbon sulfonic acid that hydroxyl replaces, six propene sulfonic acids, four amylene sulfonic acid, (wherein the Mn of polyisobutene is about 280-about 100 to polyisobutylene sulphonic acid, 000), the paraffinic hydrocarbon sulfonic acid that chlorine replaces, nitro paraffinic hydrocarbon sulfonic acid, petronaphthalene sulfonic acid, hexadecyl cyclopentyl sulfonic acid, lauryl cyclohexyl sulfonic acid, the cyclohexyl sulfonic acid that two (diisobutyl) cyclohexyl sulfonic acid and single or many paraffin replace.

17, the composition of claim 1, wherein said high alkalinity product (A) or boracic high alkalinity product (A ') are to be prepared by the organic materials (A) (I) of high alkalization and reaction medium (A) (II) with at least a, said quilt high alkalization organic materials (A) (I) is dissolved in the said reaction medium (A) (II), and is at least a compound with the following formula representative:

X in the formula ¹, X ², X ³, X ⁴Be respectively O, S or NR ³; A and b are respectively 0 or 1; R ¹, R ², R ³Be respectively alkyl, R ³Can be hydrogen.

18, the composition of claim 1, wherein said high alkalinity product (A) or boracic high alkalinity product (A ') are to be prepared by the organic materials (A) (I) of high alkalization and reaction medium (A) (II) with at least a, said quilt high alkalization organic materials (A) (I) is dissolved in the said reaction medium (A) (II), and is at least a derivative with the pentavalent phosphorous compound of following representative:

R in the formula ¹, R ², R ³Be respectively alkyl, a, b, c are respectively 0 or 1.

19, the composition of claim 1, wherein said high alkalinity product (A) or boracic high alkalinity product (A ') are to be prepared by the organic materials (A) (I) of high alkalization and reaction medium (A) (II) with at least a, said quilt high alkalization organic materials (A) (I) is dissolved in the said reaction medium (A) (II), and is at least a derivative with the trivalent phosphorous compound of following formula representative:

20, the composition of claim 1, wherein said high alkalinity product (A) or boracic high alkalinity product (A ') are to be prepared by the organic materials (A) (I) of high alkalization and reaction medium (A) (II) with at least a, said quilt high alkalization organic materials (A) (I) is dissolved in the said reaction medium (A) (II), and is a kind of compound with the following formula representative at least:

（R） _a（Ar）-（XH） _b

R is an aliphatic group in the formula, and Ar is an aryl, and X is O, S, CH ₂O or CH ₂NR ¹(R ¹Be alkyl or hydrogen), a and b are at least 1 number.

21, the composition of claim 1, wherein said high alkalinity product (A) or boracic high alkalinity product (A ') are to be prepared by the organic materials (A) (I) of high alkalization and reaction medium (A) (II) with at least a, said quilt high alkalization organic materials (A) (I) is dissolved in the said reaction medium (A) (II), and is a kind of compound with the following formula representative at least:

R is the alkyl of about 400 carbon atoms of about 4-in the formula;

R ¹Be low alkyl group, lower alkoxy, amino, aminomethyl, sulfydryl, amide group, sulfonyl amido, nitro or halogen;

A is the integer of 1-about 3;

B is 1 or 2;

C is 0 or 1.

22, the composition of claim 1, wherein said high alkalinity product (A) or boracic high alkalinity product (A ') are to be prepared by the organic materials (A) (I) of high alkalization and reaction medium (A) (II) with at least a, said quilt high alkalization organic materials (A) (I) is dissolved in the said reaction medium (A) (II), and is at least a compound with the following formula representative:

G is C(X in the formula) R, COOR, CN, R ³C=NR ⁴, CXN(R) ₂, S(O) R, SO ₂R, R ³C=R ⁴R ⁵, C ₆H ₅Or nitro (X is O or S, R, R ³, R ⁴, R ⁵Be respectively hydrogen or alkyl, and work as R ³And R ⁴During for alkyl, they can be combined together to form cyclic group;

R ¹And R ²Be respectively H, alkyl or G, and work as R ¹And R ²During for alkyl, they can be combined together to form cyclic group.

23, the composition of claim 1, wherein said high alkalinity product (A) or boracic high alkalinity product (A ') are to be prepared by the organic materials (A) (I) of high alkalization and reaction medium (A) (II) with at least a, said quilt high alkalization organic materials (A) (I) is dissolved in the said reaction medium (A) (II), and is at least a compound with the following formula representative:

R in the formula ¹, R ², R ³, R ⁴Be respectively H or alkyl separately;

R ¹And/or R ³Can be G ¹Or G ²;

R ¹And R ²And/or R ³And R ⁴Can be the alkylidene group that contains about 7 carbon atoms of about 4-together;

G ¹And G ²Be respectively C(X separately) R, COOR, C ≡ N, R ⁵C=NR ⁶, CON(R) ₂Or NO ₂; G ¹Also can be CH ₂OH(wherein X is O or S, R, R ⁵, R ⁶Be respectively H or alkyl separately);

Work as G ¹And G ²All be R ⁵C=NR ⁶The time, two R ⁶Base can be the alkylene that connects two nitrogen-atoms together;

Work as G ¹Be CH ₂OH, G ²When being COOR, can form G ¹And G ²The lactone of intramolecular condensation product;

X is the number of 1-about 8.

24, the composition of claim 1, wherein said high alkalinity product (A) or boracic high alkalinity product (A ') are to be prepared by the organic materials of high alkalization and at least a solvent that should the high organic materials that alkalizes of quilt with at least a, said solvent is a kind of mineral oil at least, Stoddard's solvent, aliphatic hydrocarbon, alicyclic hydrocarbon, aromatic hydrocarbon, halogenated aliphatic hydrocarbon, halo alicyclic hydrocarbon or halogenated aromatic.

25, the composition of claim 1, wherein said high alkalinity product (A) or boracic high alkalinity product (A ') are to prepare with at least a metal, and this metal is selected from basic metal, alkaline-earth metal, titanium, zirconium, molybdenum, iron, copper, zinc, two or more mixture of aluminium or its.

26, the composition of claim 1, wherein said high alkalinity product (A) or boracic high alkalinity product (A ') are that this metal is selected from lithium with the preparation of at least a metal, sodium, two or more mixture of potassium or its.

27, the composition of claim 1, wherein said high alkalinity product (A) or boracic high alkalinity product (A ') prepare with sodium.

28, the composition of claim 1, wherein said high alkalinity product (A) or boracic high alkalinity product (A ') are to prepare with at least a promotor, said promotor is water, Nitromethane 99Min., at least a alcohol, at least a phenol, at least a alkalimetal oxide, ammonium hydroxide, the organic acid of 8 carbon atoms of at least a as many as, spirit of salt, the mixture of two or more of salicylaldoxime or they.

29, the composition of claim 1, wherein said acidic substance are selected from carboxylamine, acetate, formic acid, boric acid, trinitromethyl, SO ₂, CO ₂, the mixture of the acid source of said acid and two or more said acid or acid source.

30, the composition of claim 1, wherein said acidic substance are SO ₂Or SO ₂The source.

31, the composition of claim 1, wherein said acidic substance are CO ₂Or CO ₂The source.

32, the composition of claim 1, wherein the metal ratio of component (A) or (A ') reaches about 40.

33, the composition of claim 1, wherein component (A ') is to prepare with at least a boron compound, this boron compound is a boron oxide, the boron oxide hydrate, boron trioxide, boron trifluoride, boron tribromide, boron trichloride, boric acid, tetraboric acid, pyroboric acid, boron trioxide or boric acid ester.

34, the composition of claim 1, wherein component (A ') prepares with boric acid.

35, the composition of claim 1, wherein component (B) is an elementary sulfur.

36, the composition of claim 1, wherein component (B) is the sulfide of at least a halogenation sulphur or phosphorus.

37, the composition of claim 1, wherein component (B) is the mixture of sulphur or at least a sulfur oxide and hydrogen sulfide.

38, the composition of claim 1, wherein component (B) is at least a aromatic series or alkyl sulfur compounds.

39, the composition of claim 1, wherein component (B) is at least a sulfurized alkene.

40, the composition of claim 1, wherein component (B) is at least a sulfurized fatty acid ester.

41, the composition of claim 1, wherein component (B) is at least a sulfurized olefinic monobasic or di-carboxylic acid fatty ester.

42, the composition of claim 1, wherein component (B) is at least a compound with the following formula representative:

S _y（（CH ₂） _xCOOR） ₂

X is the number of about 2-about 4 in the formula, and y is the integer of 1-about 6, and R is the alkyl of about 20 carbon atoms of about 4-.

43, the composition of claim 1, wherein component (B) is at least a sulfurized Diels-Alder adduct.

44, the composition of claim 1, wherein component (B) is the composition of the sulfur product preparation of at least a sulfurized terpenes or a kind of mixture that comprises at least a terpenes and at least a other olefin(e) compound.

45, the composition of claim 1, wherein component (B) is at least a compound with the following formula representative:

In the formula: R ¹, R ², R ³Be respectively H or alkyl separately;

R ¹And/or R ³Can be G ¹Or G ²;

G ¹And G ²Be respectively C(X separately) R, COOR, C ≡ N, R ⁵-C=NR ⁶, CON(R) ₂Or nitro, G ¹Also can be CH ₂OH(wherein X is O or S), R, R ⁵And R ⁶Each is H or an alkyl naturally;

Work as G ¹And G ²All be R ⁵C=NR ⁶The time, two R ⁶Can be the alkylene that connects two nitrogen-atoms together;

Work as G ¹Be CH ₂OH, G ²When being COOR, G ¹And G ²Because intramolecular condensation can form lactone;

X is the number of 1-about 8.

46, the composition of claim 1, wherein component (B) be 2,2 '-dithio two isobutyric aldehydes.

47, the composition of claim 1, wherein component (B) is at least a compound with the following formula representative:

R in the formula ¹, R ², R ³Be respectively H or alkyl; R ⁴Be H, OH or alkyl; R ⁵And R ⁶Be respectively H, alkyl or hydroxyl alkyl; Perhaps R ³And R ⁴Together and/or R ⁵And R ⁶Together and/or R ¹And R ³Together and/or R ²And R ⁴Can form cyclic group together; X is the number of 1-about 8.

48, the composition of claim 1, the product of the high alkalization of wherein said sulfuration is the active sulphur content that contacts with at least a active sulphur reductive agent of significant quantity with the sulfur product that reduces said high alkalization.

49, the composition of claim 48, wherein said active sulphur reductive agent is air and gac or water vapor, one or more boron compounds, one or more phosphites, the combination of one or more alkene, the reaction product of one or more carboxylic acid or derivatives thereofs and one or more nitrogenous compound or one or more organic hydroxy compounds, the reaction product of one or more organic hydroxy compounds of one or more carboxylic acid or derivatives thereofs and one or more nitrogenous compound or the one or more post-treatment reagents aftertreatments of one or more usefulness, perhaps the phosphorus of at least one II family metal is for dithionate.

50, the composition of claim 1, wherein said sulfuration high alkalinity product are to contact with the boric acid of significant quantity to reduce the active sulphur content of said high alkalinity sulfur product.

51, the composition of claim 1, wherein said sulfuration high alkalinity product are to contact to reduce the sulphur content of said high alkalinity sulfur product with the maleic anhydride or derivatives thereof of significant quantity and the reaction product of one or more nitrogenous compound or one or more organic hydroxy compounds.

52, the composition of claim 1, wherein said sulfuration high alkalinity product are to contact to reduce the active sulphur content of said overbasic sulfur product with the many isobutyl-s succinyl oxide or derivatives thereof of significant quantity and the reaction product of one or more nitrogenous compound or one or more organic hydroxy compounds.

53, the composition of claim 1, wherein said sulfuration high alkalinity product contacts to reduce the active sulphur content of this high alkalinity sulfur product with at least a phosphite of significant quantity.

54, the composition of claim 1, said composition further comprise a kind of sulfur-bearing high alkalinity product of unvulcanised.

55, a kind of composition, said composition comprise at least a high alkalinity thiosulphate or at least a nitrogenous high alkalinity thiosulphate.

56, a kind of composition, said composition comprise at least a high alkalinity Sulfothiorine or at least a nitrogenous high alkalinity Sulfothiorine.

57, a kind of composition, said composition comprise the boracic high alkalinity product of at least a high alkalinity thiosulphate and at least a unvulcanised.

58, a kind of composition, said composition comprise at least a sulfurized high alkalinity product, and this product is with the preparation that contacts with sulphur and/or at least a sulphur source of at least a high alkalinity product (A) or at least a boracic high alkalinity product (A ');

This high alkalinity product (A) or boracic high alkalinity product (A ') are used CO ₂Or CO ₂Source preparation, this high alkalinity product (A) or boracic high alkalinity product (A ') are with before sulphur or sulphur source (B) contacts or when contacting and the SO of significant quantity ₂Or SO ₂Source contact to replace portion C O at least ₂Or CO ₂The source.

59, a kind of composition, said composition comprise at least a sulfurized high alkalinity product that at least a high alkalinity product (A) or at least a nitrogenous high alkalinity product (A ') contact with sulphur and/or sulphur source (B) and prepare; Said high alkalinity product (A) or nitrogenous high alkalinity product (A ') are with at least a sulfonic acid, CO ₂Or CO ₂Source and at least a metal or metal base preparation, said metal is one or more metals that are selected from lithium, sodium, potassium, said high alkalinity product (A) or boracic high alkalinity product (A ') be with before sulphur or sulphur source (B) contact or in the contact with the SO of significant quantity ₂Or SO ₂The source.

60, a kind of composition, said composition comprise the sulfuration high alkaline azochlorosulfonate acid sodium of at least a high alkaline azochlorosulfonate acid sodium and sulphur and/or at least a sulphur source contact preparation;

Said high alkaline azochlorosulfonate acid sodium is with at least a sulfonic acid, sodium or at least a sodium compound and CO ₂Or CO ₂Source preparation, said high alkaline azochlorosulfonate acid sodium be with before said sulphur or sulphur source contacts or in contacting with significant quantity SO ₂Or SO ₂The source contact is to replace portion C O at least ₂

61, a kind of composition, said composition comprise at least a sulfurized high alkaline azochlorosulfonate acid sodium with at least a high alkaline azochlorosulfonate acid sodium and sulphur or at least a sulphur source contact preparation;

Said high alkaline azochlorosulfonate acid sodium is with at least a sulfonic acid, sodium or at least a sodium compound and CO ₂Or CO ₂Source preparation, said high alkaline azochlorosulfonate acid sodium be with before sulphur and/or sulphur source contacts or in contacting with the SO of significant quantity ₂Or SO ₂The source contact is to replace to the said CO of small part ₂, the equivalence ratio of sulphur or sulphur source and said high alkaline azochlorosulfonate acid sodium is about 0.65 to about 1.2.

62, a kind of composition, said composition comprises at least a sulfuration high alkalinity product with at least a high alkalinity product (A) or at least a nitrogenous high alkalinity product (A ') and sulphur and/or at least a sulphur source contact preparation, and at least a metal base activator.

Said high alkalinity product (A) and boracic high alkalinity product (A ') are to prepare with at least a acidic substance, condition is when said acidic substance are not SO 2 or SO 2 sources, and said high alkalinity product (A) or boracic high alkalinity product (A ') are the SO with significant quantity ₂Or SO ₂The source contact is to replace to the small part acidic substance.

63, a kind of composition, said composition comprises at least a sulfuration high alkalinity product and at least a phosphorated anti-wear agent with at least a high alkalinity product (A) or at least a nitrogenous high alkalinity product (A ') and sulphur and/or at least a sulphur source contact preparation;

Said high alkalinity product (A) and boracic high alkalinity product (A ') are with the preparation of at least a acidic substance, condition be when said acidic substance be not SO ₂Or SO ₂During the source, said high alkalinity product (A) or boracic high alkalinity product (A ') are and significant quantity SO ₂Or SO ₂The source contact is to replace to the said acidic substance of small part.

64, a kind of composition, said composition comprise the high-alkali boracic metal organic sulfonate of at least a sulfurized that contacts with sulphur and/or at least a sulphur source and prepare with at least a high alkalinity boracic sodium sulfonate, and this metal is selected from one or more lithiums, sodium or potassium;

This high-alkali boracic metal organic sulfonate is with at least a high-alkali metal organic sulfonate and boric acid contact preparation;

This high-alkali metal organic sulfonate is with at least a sulfonic acid and CO ₂Preparation;

This high-alkali boracic sodium sulfonate with before sulphur and/or sulphur source contact or in the contact with significant quantity SO ₂Or SO ₂The source contact is to replace to the said CO of small part ₂

65, a kind of concentrated solution, this concentrated solution comprise about 0.01% to about 90%(weight) the composition and at least a basic inert liquids in general organic solvent/thinner of claim 1.

66, a kind of lubricant or functional liquid comprise the oil that lubricant viscosity is arranged of main amount and the composition that a small amount of is improved the claim 1 of performance.

67, a kind of gear oil composition comprises the oil that lubricant viscosity is arranged of main amount and the composition of the claim 1 of extreme pressure in a small amount, wear-resistant and/or anti-oxidant improvement amount.

68, a kind of gear oil composition, what comprise main amount has the motion sticking at least about 3.5cSt(100 ℃) the oil and the composition of the claim 1 of extreme pressure, wear-resistant and/or anti-oxidant improvement amount in a small amount of main amount.

69, a kind of gear oil composition comprises the oil that lubricant viscosity is arranged of main amount, at least a viscosity modifier of viscosity modified amount and the composition of the claim 1 of extreme pressure, wear-resistant and/or anti-oxidant improvement amount in a small amount in a small amount.

70, a kind of cutting fluid comprises the cutting fluid base oil of main amount and the composition of the claim 1 of extreme pressure in a small amount, wear-resistant and/or anti-oxidant improvement amount.

71, a kind of grease composition comprises the oil that lubricant viscosity is arranged of main amount, at least a thickening material of thickening amount and the composition of the claim 1 of improvement in performance amount in a small amount.

72, a kind of fuel composition comprises the liquids in general fuel of main amount and the composition of the claim 1 of a small amount of improvement in performance amount.

73, a kind of concentrated solution comprises the composition of claim 1 and the about 80%(weight of about 20%-) water.

74, a kind of water base functional liquid comprises the water of main amount and the composition of the claim 1 of a small amount of improvement in performance amount.

75, a kind of water-fat liquor comprises the water of about 1%-about 80%, the oil of about 20%-about 90% and the composition of the claim 1 of improvement in performance amount in a small amount, all by weight.

76, a kind of composition, this combination comprise at least a sulfurized high alkalinity product, and the preparation of this product is that (A) at least a high alkalinity product or (A ') at least a alkali high alkalinity product that contains are contacted with (B) sulphur and/or at least a sulphur source; This high alkalinity product (A) and this boracic high alkalinity product (A ') are at least a by the material of high alkalization and (A) (V) at least a acid material preparation with (A) (I), condition be when acid material be not SO ₂Or SO ₂During the source, said alkaline product (A) or boracic alkaline product (A ') are the SO with significant quantity ₂Or SO ₂Source contact with the said acid material of replacing section.

77, the composition of claim 76, wherein said organic materials (A) (I) by high alkalization is to be selected from (a) at least a carboxylic acid, (b) at least a sulfur acid, (c) at least a phosphoric acid, (d) aromatics of at least a sense replacement, (e) at least a activatory methylene compound, (f) organic compound of the sense of at least a sulphur coupling replacement, (g) parent of compound (a)-(f), or (h) two or more (a)-(f) or the mixture of parent (a)-(f).

78, the composition of claim 76, wherein said organic materials (A) (I) by high alkalization are to be selected from (i) at least a carboxylic acid or acid anhydrides with the following formula representative:

(R is an alkyl in the formula), (ⅱ) at least a compound with the following formula representative:

(R in the formula ¹, R ², R ³, R ⁴, R ⁵, R ⁶Be respectively H or alkyl; R ²And R ³Can be joined together to form alicyclic ring or aromatic ring; A is the number of 0-about 4),

(ⅲ) at least one compound of representing with following formula:

R in the formula ¹And R ²Be aliphatic group, a and b are the numbers of 0-about 5, and condition is that a+b is no more than 5, and c is the number of 0-4; (ⅳ) at least one compound of representing with following formula:

R is an aliphatic alkyl in the formula, and Ar is an aromatic base, X ¹And X ²Be respectively oxygen or sulphur, a is the number of 0-about 4, and b is the number of 1-about 4, and condition is that a+b is no more than the replaceable hydrogen number on virtue nuclear or the Ar nuclear; (ⅴ) at least one compound of representing with following formula:

R is an aliphatic group in the formula, and Ar is an aromatic base, X ¹, X ²And X ³Be respectively oxygen or sulphur, a is the number of 0-about 4, and b is the number of 1-about 4, and c is the number of 1-about 4, and condition is that a+b+c is no more than the replaceable hydrogen number on virtue nuclear or the Ar nuclear; (ⅵ) at least a compound with the following formula representative:

R is an aliphatic group in the formula, and a is the number of 0-about 4, and b is the number of 1-about 4, and c is the number of 1-about 4, and condition is that a+b+c is no more than 6; Perhaps (ⅶ) their mixture.

79, the composition of claim 76, the wherein said organic materials that is alkalized (A) (I) is at least a following replacement amber acid or anhydride that is selected from: (ⅰ) at least a replacement amber acid or anhydride of being made up of substituting group and amber acidic group, substituting group wherein derives from polyolefine, the feature of said acid or anhydride is whenever the heavy substituting group of the amount 0.9 normal amber acidic group of on average having an appointment at least in its structure, (ⅱ) at least a replacement amber acid or anhydride of forming by substituting group and amber acidic group, substituting group wherein derives from polyolefine, and polyolefine total unitary about 50% is a derived from isobutylene, said polyolefinic feature is its Mn for about 1500-is about 2000, and its Mw/ Mn is about 3-about 4; The feature of said acid or anhydride is whenever the heavy on average about 1.5-about 2.5 normal amber bases of substituting group of amount in its structure, (ⅲ) at least a replacement amber acid or anhydride of forming by substituting group and amber acidic group, substituting group wherein derives from polybutene, and its total unitary butylene at least about 50% is an iso-butylene, the feature of said polybutene is that its Mn is about 800-about 1200, its Mw/ Mn value is about 3 for about 2-, and the feature of said acid or anhydride is whenever measuring the heavy about 1.2 equivalent amber acidic groups of the on average about 0.9-of substituting group in its structure.

80, the composition of claim 76, wherein said organic materials (A) (I) by high alkalization is monosulfonic acid, thionamic acid, thiosulfonic acid,-sulfinic acid, sulfenic acid, part ester sulfuric acid, sulfurous acid or thiosulfuric acid at least.

81, the composition of claim 76, wherein said organic materials by high alkalization is at least a compound of following formula:

（R _a-T-（SO ₃） _b） _cM _dor （R-（SO ₃） _b） _cM _d

R is an aliphatic group in the formula, and T is a cyclic hydrocarbon radical, and M is hydrogen or metallic cation, a, b, c, d, respectively is at least 1.

82, the composition of claim 76, wherein said high alkalization product (A) or said boracic height alkalization product (A ') are to be prepared by the organic materials of high alkalization with at least a, said organic materials by high alkalization is selected from one or more following acid or its metal-salts: mahogany acid, heavy high-viscosity lubricant sulfonic acid, Saybolt viscosity is the lubricating oil distillate deutero-sulfonic acid of about 100 seconds (100) to about 200 seconds (210), vaseline sulfonic acid, benzene, naphthalene, phenol, phenyl ether, the naphthyl disulfide thing, pentanoic, sulfonic acid and many sulfonic acid that single wax of thiophene or α-Lv Dainai or many wax replace, C ₄-C ₄₀Alkyl benzene sulphonate (ABS), the sulfuration of spermaceti phenol list sulfonic acid, two hexadecyl thiaxanthenes, dilauryl betanaphthyl sulfonic acid and two capryloyl nitro-naphthalene-monosulfonic acids.

83, the composition of claim 76, wherein said organic materials (A) (I) by high alkalization are (ⅰ) at least a compounds with the following formula representative:

X in the formula ¹, X ², X ³, X ⁴Be independent O, S or NR ³, a and b are independently 0 or 1, R ¹, R ²And R ³Be alkyl independently, R ³Can be hydrogen; (ⅱ) at least a pentavalent phosphorus derivant with the following formula representative:

R in the formula ¹, R ²And R ³Be alkyl independently, a, b and c are independently 0 or 1; (ⅲ) at least a three valent phosphors derivative with the following formula representative:

R in the formula ¹, R ²And R ³Be alkyl independently, a, b and c are independently 0 or 1.

84, the composition of claim 1, wherein said organic materials (A) (I) by high alkalization are at least a compounds with the following formula representative:

（R） _a（Ar）-（XH） _b

Wherein R is an aliphatic group, and Ar is an aromatic base, and X is O, S, CH ₂O or CH ₂NR ¹(R ¹Be hydrogen or alkyl), a and b are at least a number of 1; (ⅱ) at least a compound with the following formula representative:

R is the alkyl of about 400 carbon atoms of about 4-in the formula,

R ¹Be low alkyl group, lower alkoxy, amino, aminoethyl, sulfydryl, amide group, nitro or halogen,

A is a number of from 1 to about 3,

B is 1 or 2,

C is 0 or 1;

(ⅲ) at least a compound with the following formula representative:

Wherein G is C(X) R, COOR, CN, R ³C=NR ⁴, CXN(R) ₂, S(O) R, SO ₂R, R ³C=CR ⁴R ⁵, C ₆H ₅Or NO ₂, X is O or S, R, R ³, R ⁴, R ⁵Be independently H or alkyl, and work as R ³And R ⁴When being alkyl, they can be combined together to form cyclic group; R ¹And R ²Be H independently, alkyl or G, and work as R ¹And R ²When being alkyl, they can be combined together to form cyclic group; Or

(ⅳ) at least a compound with the following formula representative:

R in the formula ¹, R ², R ³And R ⁴Respectively be independently H or alkyl;

R ¹And/or R ³Can be G ¹Or G ²;

R ¹And R ²And/or R ³And R ⁴Can be the alkenyl that contains about 7 carbon atoms of about 4-together;

G ¹And G ²Respectively be C(X independently) R, COOR, C ≡ N, R ⁵C=NR ⁶, CON(R) ₂Or NO ₂, G ¹Also can be CH ₂OH(wherein X is O or S, R, R ⁵, R ⁶Respectively be independently H or alkyl);

Work as G ¹And G ²Be R ⁵C=NR ⁶The time, two R ⁶Base can be the alkylene that links two nitrogen-atoms together;

Work as G ¹Be CH ₂OH and G ²When being COOR, G ¹And G ²Intramolecular condensation can form lactone;

X is a number of from 1 to about 8.

85, each composition of claim 76 to 84, wherein said high alkalization product (A) or boracic high alkalization product (A ') are to prepare with at least a metal base (A) (III), and the metal that said metal base (A) (III) contains is selected from basic metal, alkaline-earth metal, titanium, zirconium, molybdenum, iron, copper, zinc, aluminium or their one or more mixture.

86, each composition of claim 76 to 85, wherein said high alkalization product (A) or boracic high alkalization product (A ') are to prepare said metal base containing metal lithium, sodium or potassium with at least a metal base (A) (III).

87, each composition of claim 76 to 86, wherein said acidic substance are selected from carboxylamine, acetate, formic acid, boric acid, trinitromethane, SO ₂, CO ₂, each sour acid source, two or more acid or the mixture of acid source.

88, each composition of claim 76 to 86, wherein said acidic substance are SO ₂Or SO ₂Source or CO ₂Or CO ₂The source.

89, each composition of claim 76 to 88, component wherein (B) is (ⅰ) elementary sulfur, (ⅱ) at least a halogenation sulphur or phosphoric sulfide, (ⅲ) mixture of sulphur or at least a sulfur oxide and hydrogen sulfide, at least a aromatics or alkyl sulfur compounds, (ⅳ) at least a sulfurized alkene, (ⅴ) at least a sulfurized fatty acid ester, (ⅵ) fatty ester of at least a olefinic monobasic of at least a sulfurized or di-carboxylic acid, (ⅶ) at least a compound with the following formula representative:

S _y（（CH ₂） _xCOOR） ₂

X is an integer of about 2 to about 5 in the formula, y is an integer of 1 to about 6, R is about 4 alkyl to about 20 carbon atoms, (ⅷ) at least a sulfurized Diels-Aielr adducts, (ⅸ) at least a sulfurized terpenes or comprise the composition of the mixture preparation of at least a terpenes and at least a other olefin(e) compound, (ⅹ) at least a compound with the following formula representative with sulfuration:

R in the formula ¹, R ², R ³, R ⁴Respectively be independently H or alkyl;

R ¹And/or R ³Can be G ¹Or G ²;

R ¹And R ²And/or R ³And R ⁴Can be to contain about 4 alkenyls together to about 7 carbon atoms;

G ¹And G ²Respectively be C(X independently) R, COOR, C ≡ N, R ⁵C=NR ⁶, CON(R) ₂Or NO ₂, G ¹Also can be CH ₂OH(X is O or S, R, R ⁵And R ⁶Respectively be independently H or alkyl);

Work as G ¹And G ²All be R ⁵C=NR ⁶The time, two R ⁶Base can be the alkyl of two nitrogen-atoms of a connection together;

Work as G ¹Be CH ₂OH, G ²When being COOR, G ¹And G ²Intramolecular condensation can form lactone.

X is the number of 1-about 8, or (ⅹ ⅰ) at least one compound with the following formula representative:

R in the formula ¹, R ²And R ³Be independently H or alkyl, R ⁴Be H, OH or alkyl, R ⁵And R ⁶Be independently H, alkyl or hydroxy alkylene, or R ³And R ⁴Together and/or R ⁵And R ⁶Together and/or R ¹And R ³Together and/or R ²And R ⁴Can form cyclic group together, x is the integer of 1-about 8.

90, the composition of claim 76-89, wherein said sulfuration high alkalinity product is that at least a active sulphur reductive agent with significant quantity is to reduce the active sulphur content of said high alkalinity sulfur product, wherein said active sulphur reductive agent is the combination of air and activated carbon or water vapour, one or more boron compounds, one or more phosphorous acid, one or more alkene, the reaction product of one or more carboxylic acid or derivatives thereofs and one or more nitrogenous compounds or one or more organic hydroxy compounds, the reaction product of one or more carboxylic acid or derivatives thereofs and one or more nitrogenous compounds or one or more organic hydroxy compounds is carried out aftertreatment with one or more post-treatment agents, the dithiophosphates of perhaps at least a II family metal.

91, the composition of claim 76-89, wherein said sulfuration high alkalinity product are to contact to reduce the active sulphur content of said high alkalization sulfur product with the boric acid or at least a phosphite of significant quantity.

92, the composition of claim 76-91, wherein said high alkalization product (A) or boracic high alkalization product (A ') are with before component (B) contact and said SO ₂Or SO ₂The source contact.

93, the composition of claim 76-91, wherein said high alkalization product (A) or boracic high alkalization product (A ') are with when component (B) contact and said SO ₂Or SO ₂The source contact.

94, each composition of claim 76-93, said composition further comprise the high alkalization of the boracic product of at least a unvulcanised, and further comprise at least a metal passivator or at least a phosphorated anti-wear agent.

95, a kind of concentrated solution, this concentrated solution comprise the about 90%(weight of about 0.01%-) claim 76-95 each composition and at least a be inert conventional liq organic solvent/thinner basically.

96, a kind of lubricant or sense liquid, it comprises each the composition of claim 76-94 of the oil that lubricant viscosity is arranged of main amount and improvement performance in a small amount.

97, a kind of lubricating grease, this lubricating grease comprise main amount the oil that lubricant viscosity is arranged, each the composition of 76-94 of at least a thickening material of thickening amount and improvement performance is in a small amount arranged.

98, a kind of fuel composition, said composition comprise each the composition of claim 76-94 of the conventional liq fuel of main amount and improvement energy in a small amount.

99, a kind of water-based functional fluid's body, this liquid comprise each the composition of claim 76-94 of the water of main amount and improvement performance in a small amount.

100, a kind of water-fat liquor, this emulsion comprise the about 80%(weight of about 1%-) the about 90%(weight of water, about 20%-) oil and improve in a small amount each the composition of claim 76-94 of performance.